WO2012175431A2 - Production de films dotés de revêtements barrières souples contenant des phyllosilicates - Google Patents

Production de films dotés de revêtements barrières souples contenant des phyllosilicates Download PDF

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WO2012175431A2
WO2012175431A2 PCT/EP2012/061520 EP2012061520W WO2012175431A2 WO 2012175431 A2 WO2012175431 A2 WO 2012175431A2 EP 2012061520 W EP2012061520 W EP 2012061520W WO 2012175431 A2 WO2012175431 A2 WO 2012175431A2
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acid
radiation
plastic film
water
coating
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WO2012175431A3 (fr
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Arno Nennemann
Stefan Sommer
Robert Maleika
Josef Breu
Michael Möller
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Bayer Intellectual Property GmbH
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Bayer Intellectual Property GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
    • C01B33/405—Clays not containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/008—Additives improving gas barrier properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds

Definitions

  • the present invention relates to the production of films with flexible, transparent berm coverings based on mixtures containing radiation-curable polymer compositions and layered silicates and also coated plastic films produced by this process.
  • High-barrier layers having an oxygen barrier of less than 10 -2 cm / (m 2 dbar) are prepared by the prior art by the deposition of mostly oxidic or nitridic metal compounds such as aluminum oxides or Siliziumoxynitriden to achieve particularly good barrier properties shadow.
  • oxidic or nitridic metal compounds such as aluminum oxides or Siliziumoxynitriden
  • multi-layered structures are used, optionally also in combination with polymeric materials. Examples of such barrier systems are described inter alia in DE-A 10 2009 000 449, US-A 2010/0151209 or WO-A. 2009/082133 described.
  • a reduction in the barrier values of polymer substrates can be achieved wet-chemically via the use of nanoscale fillers in polymer nanocomposites.
  • nanocomposite materials for example, the review article "Polymer layered silicate nanocomposites: a review” by V. Mittal in Materials 2 (3), (2009) 992.
  • barrier values of more than 1 cm / (m 2 dbar) achieved (normalized to 100 ⁇ layer thickness).
  • EP-A 1918250 discloses free-standing (substrate-free) transparent and flexible barrier layers of natural sheet silicates and film-forming polymers.
  • the barrier layers are applied from aqueous solution and then dried.
  • the layer silicate content is at least 70 wt .-% with respect to the finished barrier coating. It can thus Permeationskoeffezienten be achieved up to 0.017 cm 3 / (m 2 d bar) at 10 ⁇ layer thickness.
  • the process is disadvantageous in that the removal of the aqueous solvent is time-consuming and the barrier coatings are brittle due to the high content of phyllosilicates.
  • EP-A 2 168 918 claims non-swellable phyllosilicate tactoids which do not generally require the required surface modification for phyllosilicates for incorporation into polymer composites, as well as a process for their preparation and their use in polymer materials.
  • the barrier properties could only be slightly improved with the coatings.
  • Example I of this application describes a lithium hectorite having an aspect ratio of 20,000 (measured by AFM), from which in Example 2 a polymer-free coating was prepared.
  • the coatings described in this European application are 100% inorganic layers.
  • the object on which the present invention was based was therefore to find a simple wet-chemical process for coating plastic films with barrier coatings, in which the barrier layers have a good barrier property, in particular a good oxygen barrier property, and good flexibility.
  • the coated films should have a very good oxygen barrier property of less than 1 cm 3 / (m 2 dbar) yet be transparent and flexible, for example, for use in photovoltaic applications.
  • the process should be simpler and therefore more cost-effective than the wet-chemical processes known from the prior art, for example by shorter drying times of the applied coatings and / or by reducing the number of individual layers required for a sufficient barrier.
  • This object is achieved, surprisingly, by a process for producing a coated plastic film in which a phyllosilicate is first exfoliated in a polar solvent, then coagulated by mixing with a dispersion containing a radiation-crosslinkable polymer and the coagulum is then redispersed in an organic solvent and dispersed with this dispersion wet-chemically a coating is applied to a plastic film and dried.
  • the subject of the present invention is therefore a process for producing a coated plastic film, characterized in that
  • A) at least one layered silicate is exfoliated in a polar solvent
  • a coagulate is formed by mixing the dispersion obtained in step A) with a dispersion or solution containing at least one radiation-crosslinkable polymer in a polar solvent,
  • step D) the dispersion obtained in step C) is applied as a coating to a plastic film
  • step E) the coated film obtained in step D) is dried.
  • the layered silicate used according to the invention may be a natural or synthetic layered silicate. It is preferably a natural or synthetic layered silicate with an aspect ratio of more than 400, preferably more than 1000, particularly preferably more than 5000.
  • Phyllosilicates are a subgroup of silicate minerals.
  • SiC tetrahedra are crosslinked to layers having the composition S12O 5 .
  • octahedral layers are so-called octahedra.
  • cations are surrounded by hydroxide ions and / or oxygen in an octahedral arrangement.
  • two-layer silicates a tetrahedral layer is connected to an octahedron layer, in the three-layer silicates an octahedral layer is connected to two tetrahedral layers.
  • the layered silicates may be modified or unmodified layered silicates. Preference is given to unmodified phyllosilicates.
  • Unmodified phyllosilicates which can preferably be used for the process according to the invention are, for example, those of the mineral type montmorillonite, as contained as the main constituent in bentonite, or the bentonite itself.
  • both synthetic and naturally occurring phyllosilicates can be used, such as phyllosilicates or phyllosilicates Allevardite, amesite, beidellite, bentonite, fluorhectorite, fluoromeliugite, mica, halloysite, hectorite, illite, montmorillonite, muscovite, nontronite, palygorskite, saponite, sepiolite, smectite, stevensite, talc, vermicullite, and synthetic talcum.
  • the layered silicate used according to the invention is preferably a synthetic layered silicate, particularly preferably a synthetic smectite.
  • the smectites are three-layer silicates belonging to the group of clay minerals.
  • the layered silicate used according to the invention is a synthetic smectite of the general formula (I),
  • M m for atoms of the oxidation state 4 or 3, preferably the oxidation state 4,
  • n for metal atoms M ! the oxidation state 3 is less than or equal to 2.0 and for metal atoms M 1 of the oxidation state 2 is less than or equal to 3.0, o is less than or equal to 1, 0 and
  • the negative layer charge n is greater than 0.8 and less than or equal to 1.0.
  • M has the oxidation state 1 or 2.
  • M Li " is particularly preferred.
  • M 1 is preferably Mg 2+ , Al 3+ , Fe 2 ", Fe 3 " or a mixture of two or more of these ions.
  • M " is preferably Li + , Mg 2 " or a mixture of these cations.
  • M m is preferably a tetravalent silicon cation or a mixture of tetravalent
  • Silicon cations and Al 3+ and / or Fe 3+ particularly preferably a tetravalent silicon cation.
  • X is preferably O 2 ' .
  • Y is preferably OH " or F or a mixture of these anions, more preferably F.
  • the negative layer charge n is preferably 0.85 ⁇ n ⁇ 0.95.
  • M Li ", Na + , Mg 2+ , or a mixture of two or more of these ions
  • M ! Mg 2+ , Al 3+ , Fe 2 ", Fe 3 "or a mixture two or more of these ions
  • M n Li + , Mg 2+ or a mixture of these ions
  • M m is a tetravalent silicon cation
  • 0 Y 2 may be prepared by heating compounds of the desired metals (salts, oxides, glasses) in a stoichiometric ratio in an open or closed crucible system for the homogeneous melt, and then again be cooled.
  • Alkaline salts / alkaline earth salts, alkaline earth oxides and silicon oxides preferably binary alkali metal fluorides / alkaline earth metal fluorides, alkaline earth oxides and silicon oxides, particularly preferably IIIF, MF, MgO, quartz, can be used as starting compounds in the synthesis in the closed crucible system.
  • the quantitative ratios of the starting compounds are then, for example, from 0.4 to 0.6 mol of F in the form of the alkali metal / alkaline earth fluorides per mole of silicon dioxide and from 0.4 to 0.6 mol of alkaline earth metal oxide per mole of silica, preferably from 0.45 to 0.55 mol of F. in the form of the alkali / alkaline earth fluorides per mole of silicon dioxide and 0.45 to 0.55 moles of alkaline earth oxide per mole of silica, more preferably 0.5 mole of F " in the form of the alkaline earth alkali fluorides per mole of silica and 0.5 mole of alkaline earth oxide per mole of silica.
  • the feeding of the crucible is preferably carried out so that first the more volatile substances, then the alkaline earth oxide and finally the silicon oxide are weighed.
  • a refractory crucible of chemically inert or inert metal preferably molybdenum or platinum, is used.
  • the sealed, still open crucible is baked before being sealed in vacuo at temperatures between 200 ° C and 1100 ° C, preferably between 400 and 900 ° C to remove residual water and volatile impurities.
  • the annealing is typically performed in a high frequency induction furnace.
  • the synthesis is carried out with a temperature program adapted to the material.
  • This synthesis step is preferably carried out in a rotary graphite furnace with horizontal orientation of the axis of rotation.
  • the temperature is raised from room temperature to 1600 to 1900 ° C, preferably to 1700 to 1800 ° C, at a heating rate of 1 to 50 ° C / min, preferably 10 to 20 ° C / min.
  • a second step is heated at 1600 to 1900 ° C, preferably at 1700 to 1800 ° C.
  • the heating phase of the second step preferably lasts 10 to 240 minutes, more preferably 30 to 120 minutes.
  • the temperature is lowered at a cooling rate of 10-100 ° C / min, preferably from 30 to 80 ° C min to a value of 1100 to 1500 ° C, preferably from 1200 to 1400 ° C.
  • the temperature is lowered at a cooling rate of 0.5 to 30 ° C / min, preferably from 1 to 20 ° C / min to a value of 1200 to 900 ° C, preferably from 1100 to 1000 ° C.
  • the reduction of the heating rate after the fourth step to room temperature for example, at a rate of 0, l-100 ° C / min, preferably uncontrolled by switching off the furnace.
  • the layered silicate is obtained as a crystalline, hygroscopic solid after breaking the crucible.
  • M a , M b , M c are metal oxides and M a is equal to M b other than M c .
  • M a , M b , M c can independently of one another metal oxides, preferably L 12 O, Na 2 O, K 2 O, Rb: 0. MgO, more preferably U 2 O, Na 2 Ü, MgO be.
  • M a does not equal M b other than M c .
  • the glass step is in the desired stoichiometry of the desired salts, preferably the carbonates, more preferably L12CO3, a2COs and a silicon source such. Silicon oxides, preferably silicic acid shown.
  • the powdered ingredients are converted to a glassy state by heating and rapid cooling. Preferably, the conversion is carried out at 900 to 1500 ° C, more preferably at 1000 to 1300 ° C.
  • the heating phase in the production of the glass stage lasts 10 to 360 minutes, preferably 30 to 120 minutes, particularly preferably 40 to 90 minutes. This process is typically carried out in a glassy carbon crucible under a protected atmosphere and / or reduced pressure
  • High frequency induction heating performed.
  • the temperature is reduced to room temperature by switching off the oven.
  • the resulting glass stage is then finely ground, e.g. can be done by means of a powder mill.
  • the glass stage is added to further reactants in a weight ratio of 10: 1 to 1:10 in order to achieve the stoichiometry in A).
  • Preferred are 5: 1 to 1: 5.
  • an excess of the volatile additives of up to 10% may be added.
  • These are, for example, alkali metal or alkaline earth compounds and / or silicon compounds.
  • Preference is given to using light alkali metal and / or alkaline earth fluorides and their carbonates or oxides, and also silicon oxides.
  • Particular preference is given to using aF, LiF and / or an annealed mixture of MgCO, Mg (OH) 2 and silicic acid.
  • the mixture is heated above the melting temperature of the eutectic of the compounds used, preferably at 900 to 1500 ° C, more preferably at 1 100 to 1400 ° C.
  • the heating phase preferably lasts 1 to 240 minutes, more preferably 5 to 30 minutes.
  • the heating is carried out at a heating rate of 50-500 ° C / min, preferably with the maximum possible heating rate of the furnace.
  • the cooling after the heating phase to room temperature takes place at a rate of 1-500 ° C / min, preferably uncontrolled by switching off the furnace.
  • the product is obtained as a crystalline, hygroscopic solid.
  • the synthesis is typically carried out in a glassy carbon crucible under an inert atmosphere.
  • the heating is typically done by high frequency induction.
  • the synthetic layered silicate can preferably be freed from soluble synthesis products after the synthesis. This can be done by washing with polar solvents, preferably with aqueous or water-soluble solvents, more preferably with water, dilute acids or alkalis, methanol or mixtures thereof. The washing process is preferably carried out by means of dialysis, centrifugation or filtration.
  • the layer (s) are incorporated in a polar solvent to exfoliate the layered silicate.
  • a polar solvent for step A
  • the polar solvent in step A) is particularly preferably water, acetone, methyl ethyl ketone, at least one alcohol or a mixture comprising water, acetone, methyl ethyl ketone and / or at least one alcohol.
  • the alcohols are preferably water-soluble alcohols.
  • C 1 -C 10 -alcohols particularly preferably C 1 -C 12 -alkanols, such as, for example, Methanol, ethanol, i-propanol, n-propanol, n-butanol, i-butanol, 1-pentanol, 2-pentanol, 3-pentanol and 2-methyl-1-butanol.
  • C 1 -C 10 -alcohols particularly preferably C 1 -C 12 -alkanols, such as, for example, Methanol, ethanol, i-propanol, n-propanol, n-butanol, i-butanol, 1-pentanol, 2-pentanol, 3-pentanol and 2-methyl-1-butanol.
  • the polar solvent in step A) is very particularly preferably water or a mixture containing at least 50% by weight of water, more preferably water or a mixture containing at least 80% by weight of water.
  • the radically-crosslinkable polymer in step B) may be one which carries cationic and / or anionic groups. However, it may also be a polymer without such cationic and / or anionic groups. If anionic or nonionic polymers are used, it is preferable to add one or more coagulants to effect coagulation. These may be according to colloid-chemical textbooks salts known to the expert for electrostatic coagulation, polymers for depletion or bridging flocculation or solvents. Examples of such coagulants may be inorganic salts containing metal ions of the higher oxidation states (Me 2 ⁇ , Me 3+ ). Examples of these are Ca 2+ , Mg ?
  • the associated anions may be any inorganic anions such as carbonates, sulfates, nitrates, phosphates or halides, provided that readily water-soluble compounds result.
  • Suitable coagulants may also be organic polycations or polyanions. Examples of these are the polycationic compounds based on quaternary or protonated ternary ammonium compounds, such as poly-DADMAC (poly-dialkyldemethyl ammonium chloride), poly-PAM-co-MAPTAC (polyacrylamide-co-3-methacrylamidopropyltrimethylammonium chloride), polyethylene ethylenimines, PEE (polyethyleneethanolamine ).
  • polyanions examples are polyacrylates, polystyrene sulfonates or polyethylene sulfonates.
  • the coagulants may be the dispersion of step A), the Dispersion or solution containing at least one radiation-crosslinkable polymer in a polar solvent and / or the mixture of these two are added.
  • At least one radiation-crosslinkable polymer with cationic is preferred in step B)
  • the cationic groups may be, for example, sulfonium, phosphonium and
  • Ammonium groups preferably ammonium groups act. These may optionally be covalently bound into the polymer in their cationic or in their potentially cationic form. Covalently bound in the polymer, potentially cationic groups are understood to mean those groups which are converted by the addition of acid (s) in their cationic form. Potentially cationic groups are, for example, primary, secondary or tertiary amino groups, preferably tertiary amino groups.
  • Particularly suitable polymers which can be crosslinked by radiation are those polymers which can be crosslinked by means of electromagnetic radiation, for example by means of UV, electron, X-ray or gamma rays, preferably by means of UV or electron radiation.
  • Particularly preferred are polymers which carry ethylenically unsaturated groups which can be crosslinked by means of radiation.
  • Such ethylenically unsaturated groups may be, for example, acrylate, methacrylate, vinyl ethers, allyl ethers and maieimide groups.
  • Examples of preferred ethylenically unsaturated polymers include (meth) acrylated poly (meth) acrylates, polyurethane (meth) acrylates, polyester (meth) acrylates, polyether (meth) acrylates, epoxy (meth) acrylates, (meth) acrylated oils and unsaturated polyesters in question. (Schwalm, R., UV Coatings, 2007, Elsevier, pp. 93-139).
  • Particularly preferred ethylenically unsaturated polymers are (meth) acrylated poly (meth) acrylates or polyurethane (meth) acrylates.
  • the content of radiation-curable double bonds of the radiation-curable polymer is between 0.3 and 6.0 mol / kg, preferably between 0.4 and 4.0 mol kg, more preferably between 0.5 and 3.0 mol kg ,
  • the density of cationic groups in the radiation-curable polymer is between 0.05 and 10.0 mmol / kg, preferably between 0.1 and 5.0 mmol / kg, more preferably between 0.2 and 3.0 mmol / kg.
  • Polyurethane (meth) acrylates which carry cationic and / or potentially cationic groups are preferably used as the radiation-crosslinkable polymers.
  • polyurethane (meth) acryl late containing as structural components 1) one or more compounds having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group,
  • (Meth) acrylate in the context of this invention refers to corresponding acrylate or methacrylate functions or to a mixture of both.
  • the polyurethane (meth) acrylate has a weight average molecular weight M w of 1500 to 3000000 g / mol, preferably 2000 to 500000 g / mol, more preferably 2500 to 100000 g / mol.
  • the weight average molecular weight M was determined by gel permeation chromatography using polystyrene as standard.
  • Component 1) contains one or more compounds having at least one isocyanate-reactive group and at least one free-radically polymerizable, unsaturated group.
  • Such compounds include, for example, unsaturated group-containing oligomers and polymers such as polyester (meth) acrylates, polyether (meth) acrylates, polyether (meth) acrylates, unsaturated polyester with Allylether Modelltechniken, polyepoxy (meth) acrylates and monomers containing unsaturated groups with a molecular weight ⁇ 700 g / mol and combinations of the compounds mentioned.
  • the hydroxyl-containing polyester (meth) acrylates having an OH number in the range from 15 to 300 mg KOH / g substance, preferably from 60 to 200 mg KOH / g substance, are preferably used as component 1).
  • the first group (a) contains alkanediols or diols or mixtures of these.
  • the alkanediols have a molecular weight in the range of 62 to 286 g / mol.
  • the alkanediols are selected from the group of ethanediol, 1,2- and 1,3-propanediol, 1, 2, 1,3- and 1,4-butanediol, 1.5-Penta dio!.
  • diols are ether oxygen-containing Diols, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene, polypropylene or polybutylene glycols having a number average molecular weight M "in the range from 200 to 4000, preferably 300 to 2000, particularly preferably 450 to 1200 g / mol. Reaction products of the aforementioned diols with ⁇ -caprolactone or other lactones can also be used as diols.
  • the second group (b) contains trihydric and higher alcohols having a molecular weight in the range of 92 to 254 g / mol and / or polyethers started on these alcohols.
  • Particularly preferred trihydric and higher alcohols are glycerol, trimethylolpropane, pentaerythritol,
  • a particularly preferred polyether is the reaction product of 1 mole of trimethylolpropane with 4 moles of ethylene oxide.
  • the third group (c) contains monoalcohols.
  • Particularly preferred monoalcohols are selected from the group of ethanol, 1- and 2-propanol, 1- and 2-butanol, 1-hexanol, 2-ethylhexanol, cyclohexanol and benzyl alcohol.
  • the fourth group (d) contains dicarboxylic acids having a molecular weight in the range of 104 to 600 g / mol and / or their anhydrides.
  • Preferred dicarboxylic acids and their anhydrides are selected from the group of phthalic acid, phthalic anhydride, isophthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid,
  • the fifth group (e) contains trimellitic acid or trimellitic anhydride.
  • the sixth group (f) contains monocarboxylic acids, such as. B. benzoic acid, cyclohexanecarboxylic acid, 2-ethylhexanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, and natural and synthetic fatty acids, such as. B. Laiirin-. Myristic, palmitic, margarine, stearin, beehive,
  • Cerotin, palmitoleic, oleic, icosenic, linoleic, linolenic and arachidonic acids Cerotin, palmitoleic, oleic, icosenic, linoleic, linolenic and arachidonic acids.
  • the seventh group (g) contains acrylic acid, methacrylic acid and / or dimeric acrylic acid.
  • Suitable hydroxyl-containing polyester (meth) acrylates 1) comprise the reaction product of at least one constituent from group (a) or (b) with at least one constituent from group (d) or (e) and at least one constituent from group (g).
  • Particularly preferred constituents from group (a) are selected from the group consisting of ethanediol, 1,2- and 1,3-propanediol, 1, 4-butanediol, 1,6-hexanediol, neopentyl glycol, Cyclohexane-1, 4-dimethanol, 1,2- and 1, 4-cyclohexanediol, 2-ethyl-2-butylpropanediol, ether oxygen-containing diols selected from the group of diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol.
  • Preferred constituents from group (b) are selected from the group of glycerol, trimethylolpropane, pentaerythritol or the reaction product of 1 mol of trimethylolpropane with 4 mol of ethylene oxide.
  • Particularly preferred constituents of groups (d) and (e) are selected from the group of phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, hexahydrophytic acid, hexahydrophthalic acid anhydride, maleic anhydride, fumaric acid, succinic anhydride, glutaric acid, adipic acid, dodecanedioic acid hydrogenated dimers of the fatty acids listed under group 6 (f) and trimellitic anhydride.
  • Preferred ingredient from group (g) is acrylic acid.
  • dispersing groups which are generally known from the prior art can also be incorporated into these polyester (meth) acrylates.
  • polyethylene glycols and / or methoxypolyethylene glycols may be proportionally used as the alcohol component.
  • Alcohol-initiated polyethylene glycols, polypropylene glycols and their block copolymers, and the monomethyl ethers of these polyglycols can be used as compounds.
  • Particularly suitable is polyethylene glycol mono-methyl ether having a number average molecular weight Mn in the range of 500 to 1500 g / mol.
  • polyepoxides are the glycidyl ethers of monomeric, oligomeric or polymeric bisphenol.
  • This reaction can be used in particular to increase the OH number of the polyester (meth) acrylate, since in the polyepoxide acid reaction in each case an OI I group is formed.
  • the acid number of the resulting product is between 0 and 20 mg KOH / g, preferably between 0 and 10 mg KOH / g and more preferably between 0 and 5 mg KOH / g substance.
  • the reaction is preferably catalyzed by catalysts such as triphenylphosphine, thiodiglycol, ammonium and / or phosphonium halides and / or zirconium or tin compounds such as tin (II) ethylhexanoate.
  • polyester (meth) acrylates is described on page 3, line 25 to page 6, line 24 of DE-A 4 040 290, page 5, line 14 to page 11, line 30 of DE-A 3 316 592 and pages 123 to 135 of PKT Oldring (Ed.) In Chemistry & Technology of UV & EB Formulations For
  • hydroxyl-containing polyether (meth) acrylates which result from the reaction of acrylic acid and / or methacrylic acid with polyethers, such.
  • hydroxyl-containing polyepoxy (meth) acrylates known per se with a 011 number in the range from 20 to 300 mg KOI l g. preferably from 100 to 280 mg KOI lg, more preferably from 150 to 250 mg KOI lg or hydroxyl-containing polyurethane (meth) acrylates having an OH number in the range of 20 to 300 mg KOI l g. preferably from 40 to 150 mg KOI I g. more preferably from 50 to 140 mg KOH / g.
  • Such compounds are also described on page 37-56 in PKT Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol.
  • Hydroxyl-containing polyepoxy (meth) acrylates are based in particular on reaction products of acrylic acid and / or methacrylic acid with polyepoxides (GlycidyHSONen) of monomeric, oligomeric or polymeric bisphenol A, bisphenol F, hexanediol and / or butanediol or their ethoxylated and / or propoxylated derivatives.
  • component 1 Also suitable as component 1) are monohydroxy-functional, (meth) acrylate-containing alcohols, such as 2-hydroxy ethyl (meth) acrylate, caprolactone-extended modifications of 2-hydroxy ethyl (meth) acrylate as Bisomer Pemcure® 12A (Cognis, DE 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, containing on average monohydroxy-functional di-, tri- or penta (meth) acrylates of polyhydric alcohols, such as trimethylolpropane, Glycerol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, ditrimethylolpropane, dipent
  • reaction products of (M eth) acrylic acids with, where appropriate, dihydrazide-containing monomeric epoxy compounds can also be used as monohydroxy-functional, (meth) acrylate-containing alcohols.
  • Preferred reaction products are selected from the group of (meth) acrylic acid with glycidyl (meth) acrylate or the glycidyl ester tertiary, saturated monocarboxylic acid.
  • Tertiary, saturated monocarboxylic acids are, for example, 2,2-dimethylbutyric acid, ethylmethylbutyrate, ethylmethylpentane, ethylmethylhexane, ethylmethylheptane and / or ethylmethoxyuric acid.
  • Component 2) may be monomeric mono-, di- and / or triols each having a molecular weight of 32 to 240 g / mol, such as.
  • component 2) may contain oligomeric and / or polymeric, hydroxy-functional compounds.
  • oligomeric and / or polymeric, hydroxy-functional compounds are, for example, polyesters, polycarbonates, polyethercarbonate polyols, C2-, C3- and / or C4-polyethers, polyetheresters and / or polycarbonate-polyesters having a functionality of
  • Hydroxy-functional polyester alcohols are preferably those based on mono-, di- and tricarboxylic acids with monomeric di- and triols, as have already been enumerated as component 2), and lactone-based polyester alcohols.
  • the carboxylic acids are, for example, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, adipic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, hexahydrophthalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, hydrogenated dimers of fatty acids and saturated and unsaturated fatty acids , such as As palmitic acid, stearic acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid and their technical mixtures.
  • Hydroxy-functional polyetherols are obtainable, for example, by polymerization of cyclic ethers or by reacting alkylene oxides with a starter molecule.
  • Hydroxy-functional polycarbonates are hydroxyl-terminated polycarbonates prepared by reacting diols, lactone-modified diols or bisphenols, eg. As bisphenol A, with phosgene or carbonic diesters, such as diphenyl carbonate or dimethyl carbonate, accessible polycarbonates.
  • Hydroxy-functional polyether carbonate polyols are those as described for the construction of polyurethane dispersions in DE-A 10 2008 000478.
  • Preferred as component 2) are the polymeric, hydroxy-functional polyesters, polycarbonates, polyethercarbonate polyols, C2-, C3- and / or C4-polyethers, polyetheresters and / or polycarbonate-polyesters with an average OH-functionality of 1.8 to 2.3 preferably 1, 9 to 2,1.
  • Component 3) comprises compounds having at least one isocyanate-reactive group and optionally additionally at least one hydrophilicizing group.
  • Suitable isocyanate-reactive groups are hydroxyl and primary or secondary amino groups.
  • Hydrophilizing groups are to be understood as meaning anionic and / or potentially anionic groups as well as cationic and / or potentially cationic groups.
  • potentially anionic groups are meant those groups which are converted by the addition of base (s) by salt formation in their anionic form.
  • Potentially cationic groups are understood to mean those groups which are converted into their cationic form by addition of acid (s) by salt formation.
  • Preferred hydrophilizing groups are cationic and / or potentially cationic groups.
  • Suitable cationic groups are, for example, sulfonium, phosphonium and ammonium groups, preferably ammonium groups.
  • Potentially cationic groups are, for example, primary, secondary or tertiary amino groups, preferably tertiary amino groups.
  • Compounds with potentially cationic groups are, for example, mono-, di- and trihydroxyamines.
  • Preferred compounds containing potentially cationic groups are, for example, ethanolamine, diethanolamine, triethanolamine, 2-propanolamine, dipropanolamine, tripropanolamine, N-methylethanolamine, N-methyldiethanolamine and ⁇ , ⁇ -dimethylethanolamine.
  • Very particularly preferred compounds containing potentially cationic groups are N-methylethanolamine, N-methyldiethanolamine and N, N-dimethylethanolamine. These potentially cationic groups can be converted into the corresponding compounds by reaction with inorganic acids, such as, for example, hydrochloric acid, phosphoric acid and / or sulfuric acid, and / or organic acids, such as, for example, formic acid, acetic acid, lactic acid, methane, ethane and / or p-toluenesulfonic acid Salts and thus cationic groups are transferred.
  • the degree of neutralization is preferably between 50 and 125%. The degree of neutralization is defined as the quotient of acid and base. If the neutralization is more than 100%, more acid is added as base groups are present in the polymer.
  • Suitable anionic groups are, for example, sulfate, phosphate, carboxylate, sulfonate and phosphonate groups; suitable potentially anionic groups are, for example, carboxylic acid, Sulfonic acid and phosphonic acid groups.
  • Examples of compounds having potentially anionic groups are mono- and dihydroxycarboxylic acids, mono- and dihydroxysulfonic acids, mono- and diaminosulfonic acids, mono- and dihydroxyphosphonic acids, and mono- and diaminophosphonic acids.
  • Preferred compounds containing potentially anionic groups are selected from the group consisting of dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, N- (2-aminoethyl) alanine, 2- (2-aminoethylamino) -ethanesulfonic acid, ethylenediamine-propyl- or -butylsulfonic acid , 1, 2 or 1, 3-propylenediamine ethylsulfonic acid, 3 - (cyclohexylamino) propane-1-sulfonic acid, malic acid, citric acid, glycolic acid, lactic acid, glycine, alanine, taurine, lysine, 3,5-diaminobenzoic acid, an addition product of isophoronediamine (1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, IPDA) and acrylic acid (cf., for example, EP-A 916 647, Example
  • Butendiol and aHS0 3 as described for example in DE-A 2 446 440 on page 5-9, formula II II.
  • Particularly preferred compounds containing potentially anionic groups are carboxyl and / or sulfonic acid groups such as, for example, 2- (2-aminoethylamino) ethanesulfonic acid, 3- (cyclohexylamino) propane-1-sulfonic acid, the addition product of isophoronediamine and acrylic acid (EP 916 647 A1 , Example 1), hydroxypivalic acid and dimethylolpropionic acid.
  • component 3) contains as compounds with potentially ionic groups hydroxypivalic acid and / or dimethylolpropionic acid.
  • These potentially anionic groups can be prepared by reaction with neutralizing agents, such as triethylamine, ethyldiisopropylamine, dimethylcyclohexylamine, dimethylethanolamine, ammonia, N-ethylmorpholine, L iOl l. NaOH and / or KOI I are converted into the corresponding salts.
  • the degree of neutralization is preferably between 50 and 1 25%. The degree of neutralization is defined as the quotient of base and acid. If the neutralization is over 100%, more base is added as acid groups are present in the polymer.
  • Component 4 are polyisocyanates selected from the group of aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates or mixtures of such polyisocyanates.
  • Suitable polyisocyanates are, for example, 1, 3-cyclohexane diisocyanate, 1-methyl-2,4-diisocy anato-cyclohexane, 1-methyl-2,6-diisocyanato-cyclohexane, tetramethylene diisocyanate, 4,4 'diisocyanatodiphenylmethane, 2,4' Diisocyanatodiphenylmethane, 2,4-diisocyanatototoluene, 2,6-diisocyanatotoluene, ⁇ , ⁇ , ⁇ , ' ⁇ ,' - tetra-methyl, m- or p-xylylene diisocyanate, 1,6-hexamethylene diisocyanate
  • Preferred as component 4) are 1, 6-hexamethylene diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI) and 4,4'-diisocyanato-dicyclohexylmethane, homologues or oligomers of 1,6 Hexamethylene diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI) and 4,4-diisocyanato-dicyclohexylmethane with biuret, carbodiimide, isocyanurate, allophanate, iminooxadiazinedione and / or uretdione groups and allophanate (meth) acrylates, such as and in particular in WO-A 2006/089935, and mixtures thereof.
  • IPDI is
  • the diamines are selected from the group of ethylenediamine, 1,6-hexamethylenediamine, isophoronediamine, 1,3-, 1, 4-phenylenediamine, piperazine, 4,4'-diphenylmethanediamine, amino functional polyethylene oxides, amino functional polypropylene oxides (known under the Name Jeffamine® D series [Huntsman Corp. Europe, Zavantem, Belgium]) and hydrazine, most preferred is ethylenediamine.
  • Preferred monoamines are selected from the group of butylamine, ethylamine and amines of the Jeffamin® M series (Huntsman Corp. Europe, Zavantem, Belgium), amino-functional polyethylene oxides, amino-functional polypropylene oxides and / or amino alcohols.
  • the synthesis of the preferred polyurethane (meth) acrylates is preferably carried out by reacting components 1) to 3) and 5) with component 4) in the melt or in a non-isocyanate-reactive solvent, such as. As acetone or methyl ethyl ketone, and as is known in the art.
  • a non-isocyanate-reactive solvent such as. As acetone or methyl ethyl ketone, and as is known in the art.
  • the catalysts known in the art for urethanization such as. As dibutyltin dilaurate, tin (II) octoate and bismuth (III) octoate. In general, the mixture is heated to 30 to 60 ° C to cause the reaction to start.
  • the isocyanate content is determined at regular intervals by titration, infrared or near-infrared spectroscopy.
  • the urethanization is carried out to a residual NCO content of less than 0.3 wt .-%, particularly preferably less than 0.1 wt .-%.
  • the preferred polyurethane (meth) acrylates can be used both dissolved in a polar solvent and dispersed in step B).
  • a solution of such a polyurethane (meth) acrylate is used.
  • the polyurethane (meth) acrylate can also be converted into a corresponding aqueous dispersion in a further preferred embodiment. Any of the methods known in the art, such as emulsifier shear force, acetone, prepolymer blending, melt emulsifying, ketimine and solid spontaneous dispersing methods, or derivatives thereof, can be used to prepare such dispersions.
  • step B water, water-miscible solvents, dilute aqueous acids or bases and / or mixtures thereof may preferably be used as the polar solvent in step B).
  • the polar solvent in step B) may differ from the polar solvent in step A). But it can also be in step
  • the polar solvent in step B) is particularly preferably water, acetone, methyl ethyl ketone, at least one alcohol or a mixture comprising water, acetone, methyl ethyl ketone and / or at least one alcohol.
  • the alcohols are preferably water-soluble alcohols. These are preferably C 1 -C 10 -alcohols, particularly preferably C 1 -C 8 -alcohols, such as, for example, Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, 1-pentanol, 2-pentanol, 3-pentanol and 2-methyl-1-butanol.
  • the polar solvent in step B) is very particularly preferably water or a mixture containing at least 50% by weight of water, more preferably water or a mixture containing at least 80% by weight of water.
  • step B) can be carried out in such a way that the dispersion obtained in step A) is added to a dispersion or solution of at least one crosslinkable polymer in a polar solvent or vice versa a dispersion or solution of at least one crosslinkable Polymers are added in a polar solvent of the dispersion obtained in step A).
  • the dispersion obtained in step A) and the dispersion or solution of at least one crosslinkable polymer in a polar solvent to be combined simultaneously.
  • the organic solvent in step C) may preferably be selected from the group of ethers, alcohols, esters, ketones, amides, isrils, DMSO (dimethylsulfoxide), optionally substituted aliphatic, cycloaliphatic or aromatic hydrocarbons and other cyclic compounds or mixtures containing at least one, preferably at least two of the aforementioned act.
  • optionally substituted aliphatic hydrocarbons are the pure hydrocarbons or mixtures thereof, such as, for example, n-pentane, n-hexane, n-heptane, n-octane or petroleum ether, or halogenated hydrocarbons, such as, for example, mono-, di-, tri -, Tetra- chlorocarbon, preferably dichloromethane or chloroform in question.
  • optionally substituted aromatic hydrocarbons include the pure hydrocarbons or mixtures thereof, such as, for example, xylene, toluene, benzene or nitrophenol.
  • Suitable esters include, for example, propylene glycol monomethyl ether acetate, dibutyl adipate, ethyl acetate, hexyl acetate, heptyl acetate, tri-n-butyl citric acid, diethyl phthalate or di-n-butyl phthalate.
  • Suitable alcohols are, for example, C 1 -C 10 -alcohols, such as, for example, methanol, ethanol, n- and i-propanol, n- and i-butanol, n- and i-amyl alcohol, benzyl alcohol and 1-methoxy-2-propanol.
  • Suitable amides are, for example, dimethylformamide or dimethylacetamide.
  • Suitable ketones are, for example, acetone, methyl isobutyl ketone or cyclohexanone.
  • acetonitrile is suitable as itril.
  • Suitable ethers are, for example, aliphatic, for example diethyl ether, glycol dimer, or cycloaliphatic ethers, such as tetrahydrofuran (THF) and dioxane.
  • the organic solvent in step C) is preferably at least one ether or mixtures comprising at least one ether, very particularly preferably at least one aliphatic or cycloaliphatic ether or mixtures containing at least one aliphatic or cycloaliphatic ether.
  • At least one unsaturated monomer is added to the dispersion obtained in step C) before step D).
  • the addition of the monomer may be in the form of a dispersion or solution in an organic solvent, using as organic solvent, independently of that in step C). v all organic solvents mentioned for step C) were suitable.
  • the unsaturated monomer (s) can also be added in pure form.
  • step C) at least one unsaturated monomer may already be dispersed or dissolved in the organic solvent for redispersing the coagulum and thus be introduced into the dispersion obtained in step C).
  • such unsaturated monomers in an amount of 1 to 50 wt .-%, more preferably from 5 to 30 wt .-%, most preferably from 5 to 15 wt .-%, based on the total solids weight of the dispersion added.
  • Unsaturated monomers may preferably be acrylates or methacrylates, preferably C 1 -C 20 -alkyl acrylates or C 1 -C 10 -alkyl methacrylates, vinylaromatics, preferably C 1 -C 20 -vinyl aromatics, such as e.g.
  • Styrene vinyl toluene, ⁇ -butyl styrene or 4-n-butyl styrene, vinyl esters of carboxylic acids, preferably vinyl esters of C 1 -C 20 carboxylic acids, e.g. Vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate, vinyl ethers, preferably vinyl ethers of C1-C20 alcohols, e.g. Vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether or vinyl octyl ether, unsaturated itrils, e.g.
  • the radiation-crosslinkable monomers are particularly preferably acrylates or methacrylates, preferably C 1 -C 20 -alkyl acrylates or C 1 -C 20 -alkyl methacrylates.
  • Suitable examples of such acrylates or methacrylates are methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylates, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, n-lauryl acrylate, C 12-Cu Alkyl acrylates, 11-stearyl acrylate, n-butoxyethyl acrylate, butoxydiethylene glycol acrylate,
  • the dispersion used in step D) for coating the plastic film contains at least one suitable photoinitiator.
  • the photoinitiator may be added to the dispersion either during step C) or subsequent to step C).
  • the photoinitiator may also be covalently bonded to the crosslinkable polymer.
  • coating by radiation electromagnetic radiation is suitable whose energy, optionally with the addition of suitable photoinitiators sufficient to effect a radical polymerization of double bonds, preferably (meth) acrylate double bonds.
  • Radiation-induced polymerization preferably takes place by means of radiation having a wavelength of 400 nm to 1 ⁇ m, for example UV, electron, X-ray or gamma rays.
  • Suitable type (I) systems are aromatic ketone compounds, such as. B. benzophenones in combination with tertiary amines,
  • Alkylbenzophenones 4,4'-bis (dimethylamino) benzophenone (Michler's ketone), anthrone and halogenated benzophenones or mixtures of the types mentioned.
  • type (IQ initiators such as benzoin and its derivatives, benzil ketals, acylphosphine oxides, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bisacylphosphine oxides, phenylglyoxylic acid esters, camphorquinone, ⁇ -aminoalkylphenones, ⁇ , ⁇ -dialkoxyacetophenones and ⁇ -hydroxyalkylphenones.
  • photoinitiators which are easy to incorporate into the aqueous dispersions
  • Such products are, for example, Irgacure® 500 (a mixture of benzophenone and (1-hydroxycyclohexyl) phenyl ketone, BASF SE, Ludwigshafen, DE), Irgacure® 819 DW (phenylbis- (2 , 4,6-trimethylbenzoyl) phosphine oxide, BASF SE, Ludwigshafen, DE), Esacure® KIP EM (oligo- [2-hydroxy-2-methyl-1 - [4- (1-methylvinyl) -phenyl] -propanone], Lamberti, Aldizzate, Italy.) Mixtures of these compounds can also be used.
  • Polyurethane (meth) acrylate is z.
  • the radiation crosslinking can be carried out at any temperature, which survives the film without damage. Radiation crosslinking is advantageously carried out at from 30 to 80 ° C., since at temperatures above room temperature (23 ° C.) a higher conversion of the polymerizable double bonds in the dispersions takes place and the film remains undamaged.
  • an inert gas atmosphere ie, with exclusion of oxygen, crosslinked to a
  • the coagulum obtained in step B) is separated off from the major part of the polar solvent before the redispersion in step C). Such separation may be by filtration, centrifugation or other common method.
  • the coagulum obtained in step B) is filtered from the polar solvent before the redispersion in step C).
  • the separated coagulum may still contain polar solvent. These polar solvent residues may be wholly or partially removed either by washing with organic solvents or mixtures containing organic solvents or by drying.
  • the coagulum can also be combined with the remaining residues of the polar solvent after separation in step
  • plastic films for use in the process according to the invention are basically all plastic films.
  • a suitable plastic film for use in the method according to the invention is preferably a thermoplastic film.
  • Thermoplastic plastic films according to the invention are those films comprising at least one layer containing at least one thermoplastic material in question.
  • Such a thermoplastic plastic film may be a single-layer or multi-layer thermoplastic plastic film. In the case of a multilayer thermoplastic film as a substrate, this may be a by co-extrusion, extrusion lamination or lamination, preferably a thermoplastic film produced by co-extrusion.
  • the plastic film preferably has a thickness of 10 ⁇ to 1000 ⁇ , more preferably from 20 to 800 ⁇ , most preferably from 50 to 500 ⁇ on.
  • thermoplastics for the plastic layers are independently thermoplastics selected from polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds in question. Particularly preferred are transparent thermoplastic materials.
  • thermoplastics are polycarbonates or Copolvcarbonate based on diphenols, poly- or copolyacrylates and poly- or Copolymethacrylate example and preferably polymethylmethacrylate, poly- or copolymers with styrene such as for example and preferably transparent polystyrene or polystyrene-acrylonitrile (SAN), transparent thermoplastic polyurethanes, and polyolefins, such as for example and preferably transparent polypropylene types, or polyolefins based on cyclic olefins (for example, TOPAS ®, Hoechst), poly- or copolycondensates of terephthalic acid or naphthalenedicarboxylic acid, such as by way of example and by way of preference poly- or copolyethylene replithalate (PET or CoPET), glycol-modified PET (PETG) or poly- or copolybutylene terephthalate (PBT or CoPBT), poly--
  • thermoplastics are particularly preferably polycarbonates or copolycarbonates based on diphenols or poly- or C op olykondens ate of terephthalic acid or naphthalenedicarboxylic acid, such as by way of example and preferably poly- or copolyethylene terephthalate (PET or CoPET), glycol-modified PET (PETG) or poly or copolybutylene terephthalate (PBT or CoPBT), poly or
  • Copolyethylene naphthalate PEN or CoPEN
  • PEN Copolyethylene naphthalate
  • Suitable polycarbonates or copolycarbonates based on diphenols are, in particular, aromatic polycarbonates or copolycarbonates.
  • the polycarbonates or copolycarbonates may be linear or branched in a known manner.
  • the preparation of these polycarbonates can be carried out in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents. Details of the production of polycarbonates have been laid down in many patents for about 40 years. By way of example only Fast, “Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, D. Freitag, U. Grigo, PR Müller, I. I.
  • Suitable diphenols may be, for example, dihydroxyaryl compounds of the general formula (II)
  • Z is an aromatic radical having 6 to 34 carbon atoms, the one or more optionally substituted aromatic nuclei and aliphatic or cycloaliphatic radicals or alkylaryl or
  • Heteroatoms may contain as bridge members.
  • dihydroxyaryl compounds are resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) -diphenyl-methane, 1,1-bis- (4-hydroxyphenyl) -1-phenyl-ethane, bis- (4-hydroxyphenyl) - 1 - (1-naphthyl) -ethane, bis- (4-hydroxyphenyl) -1- (2-naphthyl) -ethane, 2,2-bis (4-hydroxyphenyl) -propane, 2,2-bis (3 , 5-dimethyl-4-hydroxyphenyl) -propane, 1,1-bis (4-hydroxyphenyl) -cyclohexane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, 1,1, - Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1'-bis (4-hydroxyphenyl)
  • dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
  • a most preferred copolycarbonate can be prepared using 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 2,2-bis (4-hydroxyphenyl) -propane.
  • Suitable carbonic acid derivatives may be, for example, diaryl carbonates of the general formula (III)
  • R 'and R "independently of one another are identical or different from hydrogen, linear or branched C 1 -C 4 -alkyl, C 7 -C 34 -alkyiaryl or C 1 -C 3 -aryl, R can furthermore also be -COO-R", where R '"is hydrogen, linear or branched Ci-C34-alkyl, C7-C34-alkylaryl or Ce-C34-aryl.
  • diaryl compounds are diphenyl carbonate, 4-tert-butylphenyl phenyl carbonate, di (4-tert-butylphenyl) carbonate, biphenyl-4-yl phenyl carbonate, di (biphenyl-4-yl) carbonate, 4- (1-methyl-1-phenylethyl) -phenyl-phenyl-carbonate, di- [4- (1-methyl-1-phenylethyl) -phenyl-carbonate and di- (methyl-salicylate) -carbonate.
  • diphenyl carbonate Both a diaryl carbonate and various diaryl carbonates can be used.
  • one or more monohydroxyaryl compound (s) may be used as a chain terminator for controlling or changing the end groups, which was not used to prepare the diaryl carbonate (s) used.
  • These may be those of the general formula (III),
  • R A is linear or branched C 1 -C 4 -alkyl, C 7 -C 34 -alkyl aryl, C 1 -C 4 -aryl or -COO-R D , where R D is hydrogen, linear or branched C 1 -C 4 -alkyl, C 7- C34 alkylaryl or C6 Cj4 aryl, and
  • R, R c are each, independently of one another or different, hydrogen, linear or branched C 1 -C 4 -alkyl, C 7 -C 34 -alkylaryl or C 6 -C 34 -aryl.
  • Suitable branching agents may be compounds having three or more functional groups, preferably those having three or more hydroxyl groups.
  • Preferred branching agents are 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-tri (4-hydroxyphenyl) ethane.
  • Suitable poly- or copolycondensates of terephthalic acid or naphthalenedicarboxylic acid in preferred embodiments of the invention are polyalkylene terephthalates or polyalkylene naphthalates.
  • Suitable polyalkylene terephthalates or polyalkylene naphthalates are, for example, reaction products of aromatic dicarboxylic acids or their reactive derivatives (for example dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
  • Preferred polyalkylene terephthalates or polyalkylene naphthalates can be prepared from terephthalic acid or aphthalene-2,6-dicarboxylic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to 10 C atoms by known methods (Kunststoff-Handbuch, Vol. VIII, p 695 ff, Karl Hanser Verlag, Kunststoff 1973).
  • Preferred polyalkylene terephthalates or polyalkylene naphthalates contain at least 80 mol%, preferably 90 mol% terephthalic acid residues or naphthalenedicarboxylic acid residues, based on the dicarboxylic acid component, and at least 80 mol%, preferably at least 90 mol% ethylene glycol and / or 1,4-butanediol radicals. based on the diol component.
  • the preferred polyalkylene terephthalates or polyalkylene naphthalates may contain, in addition to tertiary acid residues or naphthalene dicarboxylic acid residues, up to 20 mol% of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as, for example, phthalic acid, isophthalic acid, Naphthalene-2,6-dicarboxylic acid (in the case of polyalkylene terephthalates), terephthalic acid (in the case of polyalkylene naphthalates), 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic, azelaic and / or cyclohexanediacetic acid.
  • phthalic acid isophthalic acid
  • Naphthalene-2,6-dicarboxylic acid in the case of polyalkylene terephthalates
  • the preferred polyalkylene terephthalates or polyalkylene naphthalates may contain, in addition to ethylene or butane-1,4-glycol radicals, up to 20 mol% of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, z. B.
  • the polyalkylene can be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or 3- or 4-basic carboxylic acids, as z. B. in DE-A 19 00 270 and the US
  • 3,692,744 are branched.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
  • polyalkylene terephthalates which have been prepared from terephthalic acid and its reactive derivatives alone (for example their dialkyl esters) and ethylene glycol and / or butanediol-1, 4 and mixtures comprising such polyalkylene terephthalates or polyalkylene naphthalates which are composed solely of naphthalene carbinic acid and their reactive derivatives (for example their dialkyl esters) and ethylene glycol and / or 1,4-butanediol have been prepared.
  • ethylene glycol and / or 1,4-butanediol and cyclohexane-dimethanol-1,4 can be used as another diol.
  • Preferred polyalkylene terephthalates are also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components; particularly preferred copolyesters are poly (ethylene glycol / butanediol, 1,4) terephthalates.
  • the plastic substrates may be surface-activated in preferred embodiments. Such surface activation can be done, for example, physically by corona or plasma treatment or flame treatment or chemically by coating with a suitable primer layer. Such surface activation methods are known to those skilled in the art.
  • the drying is carried out in step E), preferably at least at a temperature of more than 25 ° C, preferably at least one temperature between 40 ° C and 200 ° C, more preferably at least one temperature between 50 ° C and 150 ° C.
  • the drying process can be accelerated against drying.
  • the drying can also be carried out at room temperature (RT), wherein room temperature in the context of the invention, a temperature of 20 ° C to 25 ° C is to be understood.
  • RT room temperature
  • the drying can also take place at these temperatures or correspondingly reduced temperatures at reduced pressure. This may be advantageous in particular with temperature-sensitive plastic films.
  • the coating of the coated plastic film obtained in step E) is preferably used in
  • step E) by means of irradiation, for example by means of UV, electron, X-ray or gamma rays, preferably by means of UV or electron radiation, particularly preferably by means of UV radiation, cured.
  • irradiation for example by means of UV, electron, X-ray or gamma rays, preferably by means of UV or electron radiation, particularly preferably by means of UV radiation, cured.
  • Radiation sources include, for example, UV lamps or an electron beam system, such as e.g. an electron gun, in question. Such radiation sources are known to the person skilled in the art.
  • the coated plastic film obtained in step E) is coated before or after the irradiation with at least one further, preferably one further coating composition comprising at least one radiation-crosslinkable binder.
  • the coating composition comprising at least one radiation-crosslinkable binder may additionally comprise at least one further layered silicate, in which case the above-mentioned layered silicates are suitable in particular.
  • the coated plastic film obtained in step E) can be coated before or after the deformation and / or irradiation with at least one further, preferably one further coating composition containing at least one jet-crosslinkable binder.
  • the further coating could also be applied to the coated plastic film obtained in step E) before deformation.
  • the presence of a radiation-crosslinkable binder offers the possibility of deforming the coated plastic film prior to irradiation, since the coating is still deformable in the non-crosslinked state. This is particularly advantageous over purely inorganic brittle barrier coatings in which a subsequent shaping after application to the plastic film is no longer possible.
  • Suitable radiation-crosslinkable binders are both the abovementioned radiation-crosslinkable polymers, optionally in admixture with the abovementioned unsaturated monomers, and mixtures containing at least one of the abovementioned radiation-crosslinkable polymers, optionally mixed with at least one of the abovementioned unsaturated monomers with saturated polymers, preferably saturated thermoplastic resins Polymers in question.
  • Suitable thermoplastic saturated polymers are those already mentioned above for the thermoplastic film.
  • the method according to the invention can be easily produced coated plastic films with a good oxygen barrier. Since the method of the invention has found a way to avoid the removal of aqueous solvents, the coatings can also be dried with significantly less effort. Thus, the process is significantly simplified over those processes which use aqueous based coating compositions. It is also possible with the method according to the invention to achieve very good barrier properties against oxygen of less than 1 cm / (m 2 dbar) even in the case of two layers in preferred embodiments. A complex application of a plurality of layers is not required for this purpose.
  • the present invention therefore furthermore also relates to a coated plastic film obtainable by the process according to the invention.
  • the present invention furthermore relates to a coated plastic film which has at least one base layer of at least one thermoplastic and at least one radiation-crosslinkable coating, characterized in that at least the radiation-crosslinkable coating in direct contact with the or one of the base layer (s) comprises at least one layered silicate and at least one radiation-crosslinkable binder.
  • the plastic film according to the invention comprises on the radiation-crosslinkable coating comprising at least one layered silicate and at least one radiation-crosslinkable binder which is in direct contact with the or one of the base layer (s), at least one further coating comprising at least one radiation-crosslinkable binder.
  • the suitable and preferred thermoplastics, radiation-crosslinkable binders and phyllosilicates listed above for the process according to the invention are equally suitable and preferred for the coated plastic film according to the invention.
  • the plastic film according to the invention preferably has a permeability to oxygen of less than 1 cm 7 (m 2 dbar).
  • the plastic film according to the invention or produced according to the invention is suitable for example for optical or optoelectronic applications, in particular display, lighting (fighting) or photovoltaic applications, as well as for applications in the field of Veipackeptept, especially transparent plastic packaging, such as food or beverage packaging.
  • the present invention therefore also relates to the use of the plastic film according to the invention or produced according to the invention for packaging applications or optical or optoelectronic applications.
  • NCO content The NCO content was monitored in each case according to DIN 53185 by titration.
  • the OH number was determined according to DIN 53240-2.
  • the acid number was determined according to DIN EN ISO 21 14.
  • Solids content of the polyurethane dispersion The solids content of the polyurethane dispersion was determined gravimetrically after evaporation of all nonvolatile constituents in accordance with DIN 53216.
  • Oxygen barrier The oxygen permeation was determined according to DIN 53380, Part 3, using a Mocon Ox-Tran 2/21 measuring instrument from Modern Controls, Inc. at a temperature of 23 ° C. under standard pressure with pure oxygen (> 99.95%: Linde oxygen 3.5) as permeation gas and a mixture of 95% nitrogen and 5% hydrogen (Linde forming gas 95/5) as a carrier gas. The relative humidity of measuring and carrier gas was 50%. The samples were conditioned for one to three hours prior to measurement.
  • X-ray diffraction The d (001) values were measured by measurements of the layered silicate samples on a Panalytical XPERT-Pro powder diffractometer (Cu anode, nickel filter, Cu-Ka: 1.54187 ⁇ ) in Bragg-Brentano geometry.
  • the d (001) value indicates the slice spacing.
  • the layer spacing of dried phyllosilicates is ⁇ 14 ⁇ (depending on the
  • ICP-AES Inductively Coupled Plasma Atomic Emission Spectroscopy
  • Atomic Absorption Spectroscopy Quantitative elemental analysis of the chemically digested silica samples (using a standard procedure) via AAS was performed on a Varian AA100.
  • Atomic Force Microscopy Imaging of particles under the AFM was performed on a
  • Isophorone diisocyanate Bayer MaterialScience AG, Leverkusen, DE.
  • Polypropylene film Corona-treated polypropylene film CPP 40W: Petroplast GmbH, Neuss Cloisite® Na + : Sodium montmorillonite, Southern Clay Products Inc., 1212 Church Street, Gonzales, Texas 78629, USA.
  • Li 2 C0 3 > 99%: Merck Eurolab GmbH, John-Deere-Str. 5, 76646 Bruchsal.
  • LiF > 99%: Merck Eurolab GmbH, John-Deere-Str. 5, 76646 Bruchsal.
  • Irgacure® 500 1: 1 mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone: BASF SE, Ludwigshafen, DE Ethyl methacrylate (EMA): p.a. Quality filtered over basic alumina: Sigma Aldrich GmbH, Kunststoff
  • Example 1 Preparation of a Lio, 9-Hectorite
  • a planned composition [Lio, 9] mter [Mg2, iLio, 9] oct [Su] tct O10F2
  • precursor a amorphous alkali glass
  • This glass was prepared by adding the salts L1CO3 (13.83 g) and silicic acid (S1O2 x 11H2O: 24.61 g) finely mixed and lh inductively heated at 1150 ° C under argon in a glassy carbon crucible.
  • precursor ß a second precursor (called precursor ß) was prepared by adding MgCO, Mg (OH b
  • silica (SiChxnEbO: 10.47 g) finely mixed and lh heated at 900 ° C in an aluminum oxide crucible in the chamber furnace.
  • the highly hygroscopic phyllosilicate was obtained as a colorless or grayish solid with low hardness, which already crumbled after a short time in air.
  • a very slowly sedimenting dispersion formed, which contained a large proportion of a colloidal phase, which showed little sedimentation.
  • Identification: d (001) 12.2 ⁇ (at 40% relative humidity).
  • composition from ICP-AES and AAS measurements was [Lio, 85] mter [MgysLio.ss] 00 Scanning electron microscopy (SEM) micrographs of aqueous Li-hectorite dispersions, which were slowly dried in air, hardly revealed any sheet silicate tactoids (Stapel ), but predominantly isolated, ie delaminated layers.
  • the layer silicate platelets could be well imaged due to the higher z-resolution (resolution of the sample height).
  • flexible lamellae were recognized, with lateral dimensions of up to 20 ⁇ m and a lamella height of 1 nm (aspect ratio: 20,000). Partly there were also stacks of several lamellae (less than 5).
  • the Li-hectorite was added after the synthesis in deionized water (about 20 g / l) and the soluble impurities of the synthesis were removed by dialysis against demineralized water (dialysis membrane with pore diameter 25-30 ⁇ ). The wash water of dialysis was renewed several times until the conductivity no longer rose above a value of 30 ⁇ 8. Of the washed hectorite was freeze-dried. From the dry Li-hectorite, a dispersion of the concentration of 3.0 g / l was adjusted by adding deionized water.
  • the product had a viscosity of 390 mPas at 23 ° C and an Ol I number of 128 mg KOH / g.
  • b) Preparation of the cationic, radiation-curable polyurethane acrylate dispersion 635 g of the polyester acrylate from a), 0.4 g of dibutyltin dilaurate and 0.9 g of di-tert-butyl-cresol were introduced into a reaction vessel with stirrer. At a starting temperature of 40 ° C, 214 g of isophorone diisocyanate were added dropwise with stirring, so that the temperature rose to 60 ° C. This temperature was maintained until an NCO value of 2.4% by weight had been reached.
  • Example 3a Production of a Plastic Film Coated According to the Invention with a Composite Conditioner Containing Synthetic Lio, 9-Hectorite
  • the aqueous anionic dispersion (3.0 g / l) of the layered silicate from Example 1 was mixed with the aqueous, cationic radiation-curable polyurethane acrylate dispersion from Example 2 with vigorous stirring (KPG stirrer).
  • KPG stirrer vigorous stirring
  • the dispersion in THF was admixed with 1% by weight (based on the weight of solids) of Irgacure® 500 photoinitiator, applied by means of a doctor blade (1.1 cm / s) to a polypropylene film, dried at RT for 4 to 6 hours and then at 5 cm / sec UV-crosslinked (Fusion UV Systems Inc. LC-6 benchtop conveyor, "D" -type F300S UV lamp).
  • the dry film thickness of the applied and cured coating was determined from 5-point measurements using Millitron 1204 IC (Mahr Feinmesstechnik GmbH).
  • the resulting coating contained 24.1% by weight of the layered silicate (determined from TGA analysis).
  • Example 3b Production of a Plastic Film Coated According to the Invention with a Composite Coatings Containing Commercial ⁇ -montmorillonite
  • the preparation of the composite coating was carried out analogously to Example 3a, but using the commercially available montmorillonite Cloisite® Na + .
  • the aqueous dispersion of Cloisite® Na ⁇ showed, compared to the synthetic hectorite from Example 1, a significantly smaller particle size of 370 nm (dynamic light scattering). After heterocoagulation and redispersion in THF, a stable dispersion with a smaller particle size of 340 nm (dynamic light scattering) resulted.
  • the dispersion in THF was admixed with 1% by weight (based on the weight of solids) of Irgacure® 500 photoinitiator, applied by means of a doctor blade (1.1 cm / s) to a polypropylene film, dried at RT for 4 to 6 hours and then at 5 cm / sec UV-cured (Fusion UV Systems Inc. LC-6 benchtop conveyor, "D" -type F300S UV lamp).
  • the dry film thickness of the applied and hardened coating was determined from 5-point measurements using Millitron 1204 IC (Mahr Feinmesstechnik GmbH).
  • Example 3ax The procedure was carried out as in Example 3a, but 10% by weight of ethyl methacrylate (based on the weight of solids) were added with stirring to the dispersion in THF.
  • Example 3 aax The procedure was as in Example 3a except that the coated film obtained after drying and curing was coated once more by passing the photoinitiator-dispersed dispersion in THF by means of a doctor blade (1, 1 cm / s) onto the coated side of the polypropylene film dried, dried at RT for 4 to 6 hours, and then UV cured at 5 cm / sec (Fusion UV Systems Inc. LC-6 benchtop conveyor, "D" type F300S UV lamp).
  • Example 3ay The procedure was carried out as in Example 3a except that, for dispersion in THF, an additional 10% by weight of the polyurethane acrylate solution from Example 2b in THF (based on the weight of solids) was added with stirring.
  • Example 3 aav The procedure was as in Example 3ay but the coated film obtained after drying and curing was coated once more by passing the photoinitiator-dispersed dispersion in THF by means of a doctor blade (1, 1 cm / s) onto the coated side of the polypropylene film dried, dried at RT for 4 to 6 hours, and then UV cured at 5 cm / sec (Fusion UV Systems Inc. LC-6 benchtop conveyor, "D" type F300S UV lamp).
  • Example 3bx The procedure was carried out as in Example 3b, but 10% by weight of ethyl methacrylate (based on the weight of solids) were added with stirring to the dispersion in THF.
  • Example 3bv The procedure was carried out as in Example 3b, except that 10 parts by weight of the polyurethane acrylate solution from Example 2b in THF (based on the solids weight) were added to the dispersion in THF with stirring.
  • Comparative Example 1 In Comparative Example 1, the oxygen permeation of the uncoated polypropylene film was measured (compare Table 1).
  • Comparative Example 2 In Comparative Example 2, the polypropylene film was coated with the polyurethane acrylate solution from Example 2b and its oxygen permeation was measured (see Table 1). The applied layer did not contain phyllosilicates. Comparative Example 3 Production of a Coated Plastic Film with a Pure Lio, 9 Hectorite Coating
  • the information on the layer thickness is information on the dry film thickness
  • Oxygen permeation (normalized) (layer thickness * Sauerstoffpermeation) / 100 ⁇
  • the layers of the invention also have the advantage of significantly better flexibility.
  • the coatings of Comparative Examples 3 and 4 are brittle and brittle and also have the disadvantage that they can not be applied by conventional coating techniques on the plastic films due to the lack of film-forming properties.
  • Examples 3aax and 3aay show that the turbidity of the films can be significantly reduced by an additional coating and thus the transparency can be improved.
  • the transparency of the double-coated films of Examples 3aax and 3aay of less than 10% is comparable to the transparency of the uncoated polypropylene film.

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Abstract

La présente invention concerne la production de films dotés de revêtements barrières souples et transparents à base de mélanges contenant des compositions polymères durcissables par rayonnement et des phyllosilicates, et des films en matière plastique ainsi revêtus et fabriqués selon ce procédé.
PCT/EP2012/061520 2011-06-20 2012-06-15 Production de films dotés de revêtements barrières souples contenant des phyllosilicates Ceased WO2012175431A2 (fr)

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WO2016202652A1 (fr) 2015-06-18 2016-12-22 Basf Se Copolymères composés d'exo-vinylène carbonatacrylates cycliques
CN106947036A (zh) * 2016-01-06 2017-07-14 南京金斯瑞生物科技有限公司 一种无机纳米改性氯乙烯-丙烯类衍生物-聚醚共聚物乳液及其制备方法
WO2017133935A1 (fr) 2016-02-03 2017-08-10 Basf Se Compositions aqueuses de revêtement à un composant contenant du polyuréthane et des phyllosilicates destinée à des revêtements formant barrière à l'oxygène
WO2017194330A1 (fr) 2016-05-12 2017-11-16 Basf Se Compositions aqueuses de revêtement contenant une dispersion de polymère à faible conductivité électrique et des phyllosilicates pour revêtements de barrière contre l'oxygène
EP3299402A1 (fr) 2016-09-21 2018-03-28 Henkel AG & Co. KGaA Composition à deux composants à base de composés ayant au moins deux unités de carbonate cyclique exo-vinylène
WO2018054713A1 (fr) 2016-09-21 2018-03-29 Basf Se Composés comprenant au moins deux motifs exovinylène-cyclocarbonate
EP3363840A1 (fr) 2017-02-17 2018-08-22 Henkel AG & Co. KGaA Composition de polyuréthane à deux composants comprenant un catalyseur latent
WO2018153621A1 (fr) * 2017-02-01 2018-08-30 Byk-Chemie Gmbh Lamelles de phyllosilicate ayant un haut rapport d'aspect
EP3372624A1 (fr) 2017-03-06 2018-09-12 Henkel AG & Co. KGaA Composition à un composant à base de composés ayant au moins deux unités de carbonate cyclique exo-vinylène
WO2019193104A1 (fr) 2018-04-04 2019-10-10 Altana Ag Pigments à effets à base d'hectorites colorées, et hectorites colorées revêtues et fabrication associée
EP3569597A1 (fr) 2018-05-18 2019-11-20 Basf Se Monomères comprenant au moins une unité de 4-(2-oxyethylidene)-1,3-dioxolan-2-on et leur utilisation
US10570306B2 (en) 2015-07-30 2020-02-25 Basf Se Compositions containing polyanion, ethoxylated cationic polymer and phyllosilicates for improved oxygen barrier coatings

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WO2016202652A1 (fr) 2015-06-18 2016-12-22 Basf Se Copolymères composés d'exo-vinylène carbonatacrylates cycliques
US10385152B2 (en) 2015-06-18 2019-08-20 Basf Se Copolymer made from cyclic exo-vinyl carbonate acrylates
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EP3569597A1 (fr) 2018-05-18 2019-11-20 Basf Se Monomères comprenant au moins une unité de 4-(2-oxyethylidene)-1,3-dioxolan-2-on et leur utilisation
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