WO2012175427A2 - Production de films à couches barrières souples contenant des phyllosilicates - Google Patents

Production de films à couches barrières souples contenant des phyllosilicates Download PDF

Info

Publication number
WO2012175427A2
WO2012175427A2 PCT/EP2012/061487 EP2012061487W WO2012175427A2 WO 2012175427 A2 WO2012175427 A2 WO 2012175427A2 EP 2012061487 W EP2012061487 W EP 2012061487W WO 2012175427 A2 WO2012175427 A2 WO 2012175427A2
Authority
WO
WIPO (PCT)
Prior art keywords
acid
ketone
dispersion
water
radiation
Prior art date
Application number
PCT/EP2012/061487
Other languages
German (de)
English (en)
Other versions
WO2012175427A3 (fr
Inventor
Holger Egger
Axel Schmidt
Stefan Sommer
Lars Krueger
Elvira DOSTERT
Original Assignee
Bayer Intellectual Property Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Intellectual Property Gmbh filed Critical Bayer Intellectual Property Gmbh
Publication of WO2012175427A2 publication Critical patent/WO2012175427A2/fr
Publication of WO2012175427A3 publication Critical patent/WO2012175427A3/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/42—Applications of coated or impregnated materials
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • 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
    • C08J7/048—Forming gas barrier coatings
    • 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
    • C08K3/36—Silica
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • 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 wet-chemical preparation of films with flexible, transparent berm coverings based on mixtures comprising radiation-curable polymer compositions and layered silicates and also coated plastic films produced by this process.
  • barrier layers must have barrier properties to various substances, especially gases such as oxygen or carbon dioxide, for use in a wide range of applications (from beverage packaging to OLEDs). Moreover, in many of these applications, it is important that these barrier layers be transparent and flexible.
  • barrier materials Frequently, the application of such barrier materials takes place as a layer on a substrate.
  • a common method according to the prior art is the vapor deposition of mostly oxidic or nitridic metal compound such as aluminum oxides or silicon oxynitrides in order to achieve particularly good barrier properties of significantly less than 10 -2 cm 2 (m 2 dbar).
  • Special high barrier effects can be achieved, for example, by using multi-layered structures, 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.
  • a reduction in the barrier values of polymer sub strates 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. in general, however, are with such nanocomposite materials only barrier values of more than 1 cm 3 / (m 2 dbar) reached (normalized to 100 ⁇ layer thickness).
  • barrier layers consist to a large extent of impermeable layer silicates.
  • the barrier layers consist to a large extent of impermeable layer silicates.
  • 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 here too the water-soluble polymers used can subsequently be dissolved out of these layers, as a result of which the coatings are damaged and thus their barrier properties are also destroyed.
  • the object underlying the present invention was therefore to find a simple wet-chemical method for coating plastic films with bermere coatings, in which the barrier layers have a good barrier property, in particular a good oxygen barrier property, as well as good flexibility.
  • the coated films should be transparent and flexible.
  • the barrier coatings should have improved resistance to environmental influences, especially they should not be destroyed by the influence of water by dissolving out individual constituents.
  • This object is surprisingly achieved by a process for producing a coated plastic film in which first a layered silicate is dispersed in a polar solvent and thereby preferably exfoliated, then this dispersion is combined with a dispersion or solution of a crosslinkable polymer in a polar solvent, wherein in the dispersion obtained in the combination is the weight ratio of the layered silicate to the crosslinkable polymer (s) greater than or equal to 45: 5 and less than or equal to 95: 5, and then a plastic film coated with this dispersion and dried and the coating is then crosslinked.
  • the present invention therefore provides a process for producing a plastic film with at least one barrier coating, characterized in that
  • step B) the dispersion obtained in step A) is combined with a dispersion or solution of at least one crosslinkable polymer in a polar solvent, wherein in the dispersion obtained during the mixing, the weight ratio of the phyllosilicate to the crosslinkable polymer (s) is greater than or equal to 45:55 and smaller or equal to 95: 5,
  • step D) the coated plastic film obtained in step C) is dried, and
  • step E) the coating of the coated plastic obtained in step D) is crosslinked.
  • the method according to the invention can be produced by a simple wet-chemical method plastic films with good oxygen barrier coatings, which also have good flexibility and transparency.
  • the phyllosilicates are effectively embedded in the polymer matrix, which not only has a positive influence on the barrier properties, but also provides improved resistance to environmental influences.
  • the coatings can not be destroyed by the influence of moisture by dissolving out the polymer components.
  • the layered silicate used according to the invention may be a natural or synthetic layered silicate.
  • Phyllosilicates are a subgroup of silicate minerals.
  • SiC tetrahedra are crosslinked to layers having the composition S12O 5 .
  • these tetrahedral layers are present alternately in the abovementioned layer silicates with so-called octahedral layers.
  • octahedral layers are cations surrounded by hydroxide ions and / or oxygen in octahedral arrangement.
  • a distinction is usually made between two-layer silicates and three-layer silicates. In two-layer silicates, one etch layer is connected to one octahedron layer, and in the three-layer silicates one octahedron layer is connected to two tetrahedral layers.
  • the phyllosilicates used in step A) are preferably exfoliated during the dispersion in the polar solvent.
  • the layered silicates may be modified or unmodified layered silicates. Preference is given to unmodified phyllosilicates.
  • the layered silicate is a natural or synthetic layered silicate having an aspect ratio of less than 400, preferably less than 200, more preferably from 50 to 150.
  • 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. Most preferably, it is a hectorite.
  • the polar solvent for step A it is preferable to use water, water-miscible solvents, dilute aqueous acids or bases, and / or mixtures thereof.
  • the polar solvent in step A) is particularly preferably water, at least one alcohol, at least one ketone or a mixture containing water, at least one alcohol and / or at least one ketone.
  • the alcohols are preferably water-soluble alcohols. These are preferably C 1 -C 8 -alcohols, such as, for example, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, 1-pentanoL 2-pentanol, 3-pentanol and 2-methyl-1-butanol.
  • the ketones are preferably acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone.
  • polar solvents such as amides, such as dimethylformamide or dimethylacetamide or other cyclic compounds, such as N-methyl-pyrrolidone, optionally in admixture with one or more of the aforementioned polar solvents in question.
  • 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 dispersion obtained in step A) preferably contains 0.05 to 10 wt .-%, particularly preferably 0.1 to 7 wt .-%, most preferably 1.0 to 5 wt .-% phyllosilicate, based on the total weight of dispersion.
  • the dispersion of at least one crosslinkable polymer in a polar solvent used in step B) preferably contains from 1 to 90% by weight, more preferably from 1 to 50% by weight, very preferably from 5 to 40% by weight of crosslinkable polymer (s) (e), based on the total weight of the dispersion.
  • the crosslinkable polymer in step B) may be a polymer which can be radiation-crosslinkable, thermally crosslinkable or else crosslinkable by other means.
  • Preferred crosslinkable polymers are jet-crosslinkable or thermally crosslinkable polymers, most preferably radiation-crosslinkable polymers.
  • the crosslinkable polymer in step B) may preferably be one which carries cationic and / or anionic groups. However, it may also be a polymer without such cationic and / or anionic groups.
  • the anionic groups may be, for example, sulfate, phosphate, carboxylate, sulfonate and phosphonate groups. These can optionally be covalently bound in the polymer in their ionic or in their potentially ionic form. Under covalent in Polymer-bound, potentially anionic groups are understood to mean those groups which are converted by the addition of base (s) in their ionic form.
  • Suitable radiation-crosslinkable polymers are, in particular, 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.
  • ethylenically unsaturated groups may be, for example, acrylate, methacrylate, vinyl ethers, allyl ethers and maleimide groups.
  • Examples of preferred ethylenically unsaturated polymers include (meth) acrylated poly (meth) acrylates, polyurethane (meth) acrylates, polyester (meth) acrylates, polyether (meth) acrylates,
  • 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, particularly preferably between 0.5 and 3.0 mol / kg.
  • the density of anionic 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 anionic and / or potentially anionic groups are preferably used as the radiation-crosslinkable polymers.
  • polyurethane urethane (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 w 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.
  • polyester (meth) acrylates are used as component 1) preferably the hydroxyl-containing polyester (meth) acrylates having an Ol [number in the range of 15 to 300 mg KOI I g substance, preferably from 60 to 200 mg KOI I g substance.
  • preference may be given to using those selected from two or more, preferably three or more of the total of 7 groups (a) to (g) of monomer constituents mentioned below:
  • 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 preferably selected from the group of ethanediol, 1,2- and 1,3-propanediol, 1,2-, 1,3- and 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, eopentylglycol, cyclohexane-1, 4-dimethanol, 1,2- and 1,4-
  • 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 n 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, Dipentaerythritol and sorbitol.
  • 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-propanoi, 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, hexahydrophthalic anhydride, cyclohexanedicarboxylic acid, maleic anhydride, fumaric acid, malonic acid, succinic 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. As lauric, myristic, palmitic, margarine, stearic, behenic, cerotin, palmitoleic, oleic, icosenic, linoleic, linolenic and Arachi donic acid.
  • 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. 1.6-1 lexanediol. eopentylglycol, 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 components of groups (d) and (e) are selected from the group of phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, maleic anhydride, fumaric acid, succinic anhydride, glutaric acid, adipic acid, dodecanedioic acid, hydrogenated dimers fatty acids, as they are under the 6. and trimellitic acid anhydride are preferred 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 M n in the range of 500 to 1500 g / mol.
  • polyepoxides are the glycidyl ethers of monomeric, oligomeric or polymeric bisphenol A, bisphenol F, hexanediol and / or butanediol or their ethoxylated and / or propoxylated derivatives.
  • 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 oil 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 The preparation of 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 123-135 of PKT Oldring (Ed.) In Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 2, 1991, SITA Technology, London.
  • suitable as component 1) are 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 an OH number in the range from 20 to 300 mg KOH / g, preferably from 100 to 280 mg KOH / g, more preferably from 150 to 250 mg KOH / g 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 KOH / g, more preferably from 50 to 140 mg KOH / g.
  • 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 (glycidyl compounds) 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, for example, 2-hydroxyethyl (meth) acrylate, caprolactone-extended modifications of 2-hydroxyethyl (meth) acrylate, such as Bisomer Pemcure® 12A (Cognis, DE), 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, the average monohydroxyfunktionelle di-, tri or penta (meth) acrylates of polyhydric alcohols such as trimethylolpropane, glycerol , Pentaerythritol, ditrimethylolpropane, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, ditrimethylolpropane
  • reaction products of (M eth) acrylic acids with optionally double-bond-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.
  • the listed under component 1) compounds can be used alone or as mixtures.
  • 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 which are described in DE-A 10 2008 000478 to form polyurethane dispersions.
  • component 2 are the polymeric, hydroxy-functional polyesters, polycarbonates, polyethercarbonate polyols, C2-, C3- and / or C4-polyethers, polyetheresters and / or polycarbonate-polyesters having an average OH-functionality of 1.8 to 2.3, particularly preferred 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
  • 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 replaced by the addition of acid (s)
  • Salt formation are converted into their cationic form.
  • Preferred hydrophilizing groups are anionic and / or potentially anionic 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, methylethanolamine, 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.
  • inorganic acids such as, for example, hydrochloric acid, phosphoric acid and / or sulfuric acid
  • 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 sulfate, phosphate, carboxylate, sulfonate and phosphonate groups; suitable potentially anionic groups are, for example, carboxylic acid, sulfonic acid and phosphonic acid groups.
  • suitable 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-amino-ethylamino) -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
  • 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 anionic groups hydroxypivalic acid and / or dimethylolpropionic acid.
  • These potentially anionic groups can be converted into the corresponding salts by reaction with neutralizing agents, such as triethylamine, ethyldiisopropylamine, dimethylcyclohexylamine, dimethylethanolamine, ammonia, N-ethylmorpholine, LiOH, NaOH and / or KOI I.
  • neutralizing agents such as triethylamine, ethyldiisopropylamine, dimethylcyclohexylamine, dimethylethanolamine, ammonia, N-ethylmorpholine, LiOH, NaOH and / or KOI I.
  • the degree of neutralization is preferably between 50 and 125%.
  • 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-diisocyanato-cyclohexane, 1-methyl-2,6-diisocyanato-cyclohexane, tetramethylene diisocyanate ene, 4,4 'diisocyanatodiphenylmethane, 2,4' -Diisocyanatodiphenylmethane, 2,4-diisocyanatototoluene, 2,6-diisocyanatototoluene, ⁇ , ⁇ , ⁇ , ' ⁇ ,' -Tetra-methyl, m- or p-xylylene diisocyanate, 1, 6-hexamethylene diis
  • IPDI Isophorone diisocyanate
  • TIN 4-isocyanatomethyl-1,8-octane diisocyanate
  • homologues or oligomers of these enumerated polyisocyanates Biuret, carbodiimide, isocyanurate, allophanate, iminooxadiazinedione and / or uretdione groups and mixtures thereof.
  • 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 -Hexamethylendiisocyanat, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (I s o cy ophorondiis Anat or IPDI) and 4,4 '- diisocyanato-dicyclohexylmethane with biuret, carbodiimide, isocyanurate, allophanate, Iminooxadiazindion- and / or uretdione groups and allophanate (meth) acrylates, such as, for example and in particular in WO-A 2006/
  • the diamines are preferably selected from the group consisting 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.
  • 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 NGO 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.
  • 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.
  • emulsifier shear force 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.
  • emulsifier shear force such as emulsifier shear force, acetone, prepolymer blending, melt e
  • Acetone process Particularly preferred is the acetone process.
  • Suitable thermally crosslinkable polymers are, for example, self-crosslinking polyacrylates, or 2-component systems containing an oil [-functional polymer and isocyanate, where the isocyanate may also be blocked (cf., for example, U. Meier-Westhues, Polyurethane, Vincentz Network, Hannover, 2007, pp. 25-63).
  • polar solvent in 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). However, the same polar solvents can also be used in step A) and B).
  • the polar solvent in step B) is particularly preferably water, at least one alcohol, at least one ketone or a mixture containing water, at least one alcohol and / or at least one ketone.
  • the alcohols are preferably water-soluble alcohols. Preferably, these are C 1 -C 8 alcohols, e.g. Ethanol, i-propanol, n-propanol, n-butanol. i-butanol, 1-pentanol, 2-pentanol, 3-pentanol and 2-methyl-1-butanol.
  • the ketones are preferably acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone.
  • polar solvents such as amides, e.g. Dimethylformamide or dimethylacetamide or other cyclic compounds, e.g. N-methyl-pyrrolidone, optionally in admixture with one or more of the aforementioned polar solvents in question.
  • the polar solvent in step B) is very particularly preferably at least one ketone or a mixture comprising at least 50% by weight of at least one ketone, more preferably at least one ketone or a mixture containing at least 80% by weight of at least one ketone.
  • the ketones are preferably Acteon, Methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone.
  • An especially preferred ketone is acetone.
  • the weight ratio of the layered silicate to the crosslinkable polymer (s) in the dispersion obtained in step B) is greater than or equal to 45:55 and less than or equal to 90:10.
  • the dispersion obtained in step B) by combining preferably contains 0.025 to 9% by weight.
  • % more preferably 0.05 to 5 wt .-%, most preferably 0.5 to 4 wt .-% phyllosilicate, based on the total weight of the dispersion.
  • the combining in 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 conversely a dispersion or solution of at least one crosslinkable polymer in a polar solvent of step A ) are added.
  • 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.
  • At least one crosslinkable monomer preferably at least one unsaturated monomer
  • the addition of the monomer may be in the form of a dispersion or solution in a solvent.
  • the unsaturated monomer (s) can also be added in pure form.
  • 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.
  • suitable solvents for the monomer or monomers are organic solvents, for example those selected from the group consisting of ethers, alcohols, esters, ketones, amides, isrils, DM SC ) (dimethylsulfoxide), optionally substituted aliphatic, cycloaliphatic or aromatic Kohlenwas s er sto ffe and other cyclic compounds or mixtures containing at least one, preferably at least two of the aforementioned.
  • polar organic solvents such as, for example, the alcohols, ketones, amides or other cyclic compounds mentioned above for step A) or B).
  • Unsaturated monomers may preferably be acrylates or methacrylates, preferably C 1 -C 10 -alkyl acrylates or C 1 -C 2 0 -alkyl methacrylates, vinylaromatics, preferably C 1 -C 20 vinylaromatics, for example styrene, vinyltoluene, ⁇ -butylstyrene or 4-n-butylstyrene, vinyl esters of carboxylic acids, preferably vinyl esters of C 1 -C 20 -carboxylic acids, such as vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate, vinyl ethers, preferably vinyl ethers of C1-C20-alcohols, such as vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether or vinyl octyl ether, unsaturated nitriles such as acrylonitrile or methacrylonitrile, or an alkene having
  • 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, Cn-Cjs Alkyl acrylates, n-stearyl acrylate, n-butoxyethyl acrylate, butoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
  • the dispersion used in step C) for coating the plastic film contains at least one suitable initiator for the crosslinking, preferably at least one suitable photoinitiator.
  • the initiator preferably photoinitiator, may be added to the dispersion either during step B) or subsequent to step B).
  • the photoinitiator may also be covalently bonded to the crosslinkable polymer.
  • suitable initiators are, for example, the catalysts known in the prior art for urethanization, such as, for example, As dibutyltin dilaurate, tin (II) octoate and bismuth (III) octoate.
  • step E) the crosslinking of the coating takes place via radiation curing
  • electromagnetic radiation is suitable for this purpose, the energy of which, if appropriate with the addition of suitable Photoinitiators is sufficient to effect a radical polymerization of double bonds, preferably (meth) acrylate double bonds.
  • the radiation-induced polymerization preferably takes place by means of radiation having a wavelength of 400 nm to 1 ⁇ m, such as, 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 (II) 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 , Preference is given to 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], from Lamberti, Aldizzate, Italy). It is also possible to use mixtures of these compounds.
  • photoinitiator it may be advantageous to covalently attach the photoinitiator to the crosslinkable polymer.
  • polyurethane (meth) acrylate dispersions z.
  • polar solvents such as.
  • acetone and isopropanol can be used.
  • 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.
  • the coated plastic film obtained in step D) is crosslinked under an inert gas atmosphere, ie, with the exclusion of oxygen, in order to prevent inhibition of free-radical crosslinking by oxygen. It is also possible to deform the coated plastic film obtained in step D) before irradiation.
  • 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.
  • plastic films for use in the process according to the invention are basically all plastic films.
  • a suitable plastic film for use in the inventive method 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.
  • a multilayer thermoplastic film as a substrate it may be one by co-extrusion, extrusion lamination or lamination, preferably a co-extruded thermoplastic film.
  • 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 copolycarbonates based on diphenols, poly- or copolyacrylates and poly- or co-polyethacrylates such as, by way of example and by way of preference, polymethyl methacrylate, poly- or copolymers with styrene such as, by way of 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 Naphthahndic arb ons äure such as for example and preferably poly- or copolyethylene terephthalate (PET or CoPET) glycol-modified PET (PETG) or poly- or copolybutylene
  • thermoplastic materials with high transparency and low Haze value, since these are particularly suitable for optical or optoelectronic applications, such as in display applications.
  • thermoplastics are special 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) or mixtures of the foregoing.
  • 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.
  • polycarbonates can be carried out in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents.
  • Plastics Handbook volume 3/1, polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser
  • Suitable diphenols may be, for example, dihydroxyaryl compounds of the general formula (II)
  • Heteroatoms may contain as bridge members.
  • Particularly preferred 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,
  • 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 '"C7-C34-Alkyiaryl or Ce-C34-aryl independently of one another identical or different and represent hydrogen, linear or branched Ci-C34 alkyl, R furthermore also C and R' OO-R '" R.
  • R can be where R '"is hydrogen, linear or branched Ci-C34-alkyl, C7-C34-alkylaryl or C6-C34-aryl.
  • diaryl compounds are diphenyl carbonate, 4-tert-butylphenyi-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.
  • 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 Ci-C34-alkyl, C7-Cj4-alkylaryl, Ce-C34-aryl or -COO-R D , where R D is hydrogen, linear or branched Ci-C34-alkyl, C7-C34 - alkylaryl or Ce-C34-aryl, and
  • R ". R c are the same or different and represent hydrogen, linear or branched Ci-C34 alkyl, C7-C34-alkylaryl, or Ce-C M aryl independently.
  • 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 naphthalene-dicarboxylic 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 naphthalene-2,6-dicarboxylic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to 10 carbon atoms by known methods (Kunststoff-Handbuch, Bd 695 ff, Karl Hanser Verlag, Kunststoff 1973).
  • Preferred polyalkylene terephthalates or polyalkylene naphthalates contain at least 80 mol%, preferably 90 mol%, of higher ethereal or naphthalenedicarboxylic acid residues, based on the dicarboxylic acid component, and at least 80 mol%, preferably at least 90 mol%, of ethylene glycol and / or 1,4-butanediol. residues. 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 C atoms or cycloaliphatic diols having 6 to 21 C 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 US 3,692,744 are branched.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythnt.
  • 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 carried out, for example, physically by corona or plasma treatment or blazing or chemically by coating with a suitable primer layer. Such surface activation methods are known to those skilled in the art.
  • the coating of the plastic film in step C) can be carried out by conventional and known to those skilled assbezelsmethoden.
  • the drying in step D) is carried out at a temperature of more than 25 ° C, preferably at a temperature between 40 ° C and 200 ° C, more preferably at a temperature between 50 ° C and 150 ° C.
  • the drying in step D) can be carried out by conventional methods.
  • suitable and preferred are drying in a drying oven, circulating air drying, infrared drying or other drying methods known to the person skilled in the art.
  • these drying processes can also take place when passing through a suitably equipped drying line.
  • the coating of the coated plastic film obtained in step D) is preferably cured after step D) in step E) by irradiation, preferably by UV or electron radiation, more preferably by UV radiation.
  • irradiation preferably by UV or electron radiation, more preferably by UV radiation.
  • crosslinking of the jet-crosslinkable polymers if appropriate also with the unsaturated monomers additionally present in the coating, takes place.
  • radiation sources are, for example, UV lamps or an electron beam system, such. an electron gun, in question. Such radiation sources are known to the person skilled in the art.
  • the coated film obtained in step D) preferably has, after drying, a coating having a dry film thickness of from 0.1 to 25 ⁇ m, particularly preferably from 0.5 to 20 ⁇ m, very particularly preferably from 1 to 15 ⁇ m.
  • the coated plastic film obtained in step D) is coated before or after, preferably after crosslinking, with at least one further, preferably one further coating composition containing at least one crosslinkable, preferably radiation-crosslinkable binder.
  • the coating composition comprising at least one crosslinkable, preferably jet-crosslinkable binder may additionally comprise at least one layered silicate, in which case the above-mentioned layered silicates are suitable in particular.
  • both coatings can then be advantageously cured in a crosslinking process, preferably irradiation process.
  • Suitable crosslinkable, preferably radiation-crosslinkable binders are both the abovementioned crosslinkable, preferably jet-crosslinkable polymers, optionally in admixture with the abovementioned unsaturated monomers, and mixtures containing at least one of the abovementioned crosslinkable, preferably radiation-crosslinkable polymers, optionally in admixture with at least one of the above unsaturated monomers mentioned with saturated polymers, preferably saturated thermoplastic polymers in question.
  • Suitable thermoplastic saturated polymers are those already mentioned above for the thermoplastic film.
  • the coated film can also be deformed, wherein the shape can be fixed by the subsequent crosslinking in step E).
  • the process according to the invention makes it possible to produce coated plastic films with a sufficiently good oxygen barrier for many applications in a simple manner. A complex application of a plurality of layers is not required for this purpose.
  • the process according to the invention offers the possibility of producing coatings with good oxygen barrier properties by embedding the preferably exfoliated phyllosilicates in a crosslinked polymer matrix, which have good resistance to environmental influences. For example, by the action of moisture, the polymers can no longer be dissolved out of the crosslinked polymer matrix.
  • the use of radiation-crosslinkable polymers together with the layer silicates for the barrier coating enables an efficient distribution of the phyllosilicates in the barrier coating and thus an improvement in the barrier properties.
  • the barrier coatings remain flexible, so that fractures caused by brittleness, which would destroy or at least significantly reduce the barrier property, can be significantly reduced or avoided.
  • the present invention therefore furthermore also relates to a coated plastic film obtainable by the process according to the invention.
  • 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 20 cm 3 / (m 2 dbar).
  • the plastic film according to the invention or produced according to the invention is suitable for example for optical or opto-electronic applications, in particular display, lighting (fighting) or photovoltaic applications, as well as for applications in the field of packaging, in particular transparent plastic packaging, such. 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.
  • the NCO content was monitored in each case according to DIN 53185 by titration.
  • the solids content of the polyurethane dispersion was determined gravimetrically after evaporation of all nonvolatile constituents in accordance with DIN 53216.
  • the OH number was determined according to DIN 53240-2.
  • Desmodur® 3300 hexamethylene diisocyanate trimer, Bayer MaterialScience AG, Leverkusen, DE
  • 30.1 g of 1, 4-butanediol, 1.1 g of 2,6-di-tert-butyl-cresol and 0.6 g of dibutyltin dilaurate were dissolved in 593 g of acetone, and with stirring at 60 ° C, a dropwise addition of 277 g of 2-hydroxyethyl acylate.
  • reaction temperature was maintained at 60 ° C to an NCO value of 3.6% by weight, 51.3 g Dimetyhlolpropion Acid were added and further stirred at 60 ° C until an NCO value of less than 0.1 wt .-% was reached.
  • Example 1b Preparation of the anionic, radiation-curable polyurethane acrylate solution lb
  • Example 2a Preparation of the parent dispersion Schichtsiiicat / polyurethane acrylate solution 2a
  • Step Example! 2b Preparation of the parent dispersion of phyllosilicate / polyurethane acrylate solution 2b
  • Example 3 Preparation of phyllosilicate / polymer coatings on polycarbonate films
  • a corona-treated polycarbonate films (Makrofol® DE 1 - 1. thickness 175 ⁇ , size about DIN A4, Bayer MaterialSciene AG, Leverkusen) were briefly treated with an antistatic fan to reduce static charges. Subsequently, 25 ml of the dispersion from Example 2a or 2b were applied and applied using a doctor blade machine (wet film thickness 500 ⁇ m, doctor blade speed approx. 100 mm / s). Subsequently, the film was dried at 70 ° C. for about 20 minutes in a circulating air dryer. This was followed by UV curing at 2 x 800 mJ / cm 2 on an installation IST-UV type UE-600-2 TR. The dry film thickness of the cured coating was about 8 ⁇ (determined from SEM image).
  • the gas permeability measurements for oxygen were carried out in accordance with DIN 53380 Part 1 with the following parameters: default pressure: 1000 mbar, humidity: dry, temperature 23 ° C, detection of pressure transducer from MKS.
  • OTR oxygen permeabilities
  • SEM images of the coatings according to the invention showed the good plane-parallel alignment of the exfoliated layers of the layered silicate in these layers.

Abstract

La présente invention concerne la production par voie humide de films à couches barrières transparentes souples à base de mélanges contenant des compositions polymères durcissables par rayonnement et des phyllosilicates, ainsi que des films plastiques à revêtement produits selon ledit procédé.
PCT/EP2012/061487 2011-06-20 2012-06-15 Production de films à couches barrières souples contenant des phyllosilicates WO2012175427A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11170551 2011-06-20
EP11170551.3 2011-06-20

Publications (2)

Publication Number Publication Date
WO2012175427A2 true WO2012175427A2 (fr) 2012-12-27
WO2012175427A3 WO2012175427A3 (fr) 2013-04-04

Family

ID=46320958

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/061487 WO2012175427A2 (fr) 2011-06-20 2012-06-15 Production de films à couches barrières souples contenant des phyllosilicates

Country Status (1)

Country Link
WO (1) WO2012175427A2 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104789104A (zh) * 2014-01-17 2015-07-22 佛山市顺德区博宜防腐涂料科技有限公司 高机械性能含羟基聚氨酯共聚丙烯酸水性工业漆
WO2016202652A1 (fr) 2015-06-18 2016-12-22 Basf Se Copolymères composés d'exo-vinylène carbonatacrylates cycliques
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
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
CN110003753A (zh) * 2019-04-25 2019-07-12 哈尔滨工业大学无锡新材料研究院 一种用于双向拉伸聚酯薄膜的高阻隔涂料及其制备方法
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
CN113929867A (zh) * 2021-09-15 2022-01-14 深圳市力合科创股份有限公司 铸膜液及其制备方法、以及高阻隔复合膜及其制备方法
CN115572530A (zh) * 2022-09-08 2023-01-06 浙江锦美材料科技有限公司 一种用于iml工艺的硬化涂层及其制备方法

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1900270A1 (de) 1968-01-04 1969-11-06 Rhodiaceta Neue thermoplastische Formmassen
DE2407674A1 (de) 1973-03-30 1974-10-10 Tokyo Kosei Kaken Co Fahrbare vorrichtung zum schleifen und reinigen von boeden
DE2407776A1 (de) 1974-02-19 1975-09-04 Licentia Gmbh Schaltung zur regelung der betriebsspannung fuer die transistor-zeilenendstufe eines fernsehempfaengers
DE2446440A1 (de) 1974-09-28 1976-04-08 Bayer Ag Verfahren zur herstellung von polyurethanen
DE2715932A1 (de) 1977-04-09 1978-10-19 Bayer Ag Schnellkristallisierende poly(aethylen/alkylen)-terephthalate
DE3316592A1 (de) 1983-05-06 1984-11-08 Basf Ag, 6700 Ludwigshafen Verwendung zur herstellung von (meth) acrylsaeureestern und deren verwendung
DE4040290A1 (de) 1990-12-17 1992-07-02 Synthopol Chemie Dr Koch Verfahren zur herstellung von acryloyl-funktionellen polyestern (polyesteracrylaten)
EP0916647A2 (fr) 1997-11-13 1999-05-19 Bayer Ag Agent hydrophile, procédé pour sa préparation et son utilisation comme agent dispersant pour des dispersions aqueuses de polyuréthane
EP0928799A1 (fr) 1998-01-07 1999-07-14 Bayer Ag Utilisation d'isocyanates particuliers pour la préparation des revêtements aqueux de PUR
WO2006089935A1 (fr) 2005-02-24 2006-08-31 Basf Aktiengesellschaft Dispersions de poluyrethanne aqueuses durcissables par rayonnement
EP1918250A1 (fr) 2005-08-03 2008-05-07 National Institute of Advanced Industrial Science and Technology Film transparent
DE102008000478A1 (de) 2007-03-05 2008-09-11 Basf Se Polyurethan-Dispersionen mit Polyethercarbonatpolyolen als Aufbaukomponente
WO2009082133A2 (fr) 2007-12-24 2009-07-02 Choongwae Corporation Film multicouche à barrière élevée pour produit fonctionnel de solution médicale
US20100151209A1 (en) 2008-12-15 2010-06-17 Industrial Technology Research Institute Organic/inorganic multi-layered gas barrier film
DE102009000449A1 (de) 2009-01-28 2010-08-05 Evonik Degussa Gmbh Transparente, witterungsbeständige Barrierefolie

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5700560A (en) * 1992-07-29 1997-12-23 Sumitomo Chemical Company, Limited Gas barrier resin composition and its film and process for producing the same
US7303797B1 (en) * 1999-02-16 2007-12-04 E.I. Du Pont De Nemours And Company Gas barrier coating system for polymeric films and rigid containers
JP5466802B2 (ja) * 2004-10-18 2014-04-09 三井化学株式会社 水性ポリウレタン樹脂及び積層フィルム
US20090098395A1 (en) * 2007-10-15 2009-04-16 Pang Chia Lu Barrier coating for thermoplastic films
CN102597076B (zh) * 2009-11-24 2014-11-19 花王株式会社 膜状体及其制备方法以及用于形成该膜状体的水性分散液

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1900270A1 (de) 1968-01-04 1969-11-06 Rhodiaceta Neue thermoplastische Formmassen
US3692744A (en) 1968-01-04 1972-09-19 Rhodiaceta Injection molded branched polyesters
DE2407674A1 (de) 1973-03-30 1974-10-10 Tokyo Kosei Kaken Co Fahrbare vorrichtung zum schleifen und reinigen von boeden
DE2407776A1 (de) 1974-02-19 1975-09-04 Licentia Gmbh Schaltung zur regelung der betriebsspannung fuer die transistor-zeilenendstufe eines fernsehempfaengers
DE2446440A1 (de) 1974-09-28 1976-04-08 Bayer Ag Verfahren zur herstellung von polyurethanen
DE2715932A1 (de) 1977-04-09 1978-10-19 Bayer Ag Schnellkristallisierende poly(aethylen/alkylen)-terephthalate
DE3316592A1 (de) 1983-05-06 1984-11-08 Basf Ag, 6700 Ludwigshafen Verwendung zur herstellung von (meth) acrylsaeureestern und deren verwendung
DE4040290A1 (de) 1990-12-17 1992-07-02 Synthopol Chemie Dr Koch Verfahren zur herstellung von acryloyl-funktionellen polyestern (polyesteracrylaten)
EP0916647A2 (fr) 1997-11-13 1999-05-19 Bayer Ag Agent hydrophile, procédé pour sa préparation et son utilisation comme agent dispersant pour des dispersions aqueuses de polyuréthane
EP0928799A1 (fr) 1998-01-07 1999-07-14 Bayer Ag Utilisation d'isocyanates particuliers pour la préparation des revêtements aqueux de PUR
WO2006089935A1 (fr) 2005-02-24 2006-08-31 Basf Aktiengesellschaft Dispersions de poluyrethanne aqueuses durcissables par rayonnement
EP1918250A1 (fr) 2005-08-03 2008-05-07 National Institute of Advanced Industrial Science and Technology Film transparent
DE102008000478A1 (de) 2007-03-05 2008-09-11 Basf Se Polyurethan-Dispersionen mit Polyethercarbonatpolyolen als Aufbaukomponente
WO2009082133A2 (fr) 2007-12-24 2009-07-02 Choongwae Corporation Film multicouche à barrière élevée pour produit fonctionnel de solution médicale
US20100151209A1 (en) 2008-12-15 2010-06-17 Industrial Technology Research Institute Organic/inorganic multi-layered gas barrier film
DE102009000449A1 (de) 2009-01-28 2010-08-05 Evonik Degussa Gmbh Transparente, witterungsbeständige Barrierefolie

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
"Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints", vol. 2, 1991, SITA TECHNOLOGY
"Kunststoff-Handbuch", vol. VIII, 1973, KARL-HANSER-VERLAG, pages: 695 FF
"Methoden der Organischen Chemie, Houben-Weyl", vol. E20, 1987, GEORG THIEME VERLAG
D. FREITAG; U. GRIGO; P. R. MÜLLER; H. NOUVERTNE; BAYER AG: "Encyclopedia of Polymer Science and Engineering", vol. 11, 1988, article "Polycarbonates", pages: 648 - 718
GRUNLAN ET AL., THIN SOLID FILMS, vol. 516, 2008, pages 4819
KOTOV ET AL.: "beispielsweise besonders stabile freistehende, d.h. substratfreie, Schichtsilicat-PVA-Filme", SCIENCE, vol. 318, 2007, pages 80
R. SCHWALM: "UV Coatings", 2007, ELSEVIER, pages: 93 - 139
REVIEWARTIKEL; V. MITTAL: "Polymer layered silicate nanocomposites: a review", MATERIALS, vol. 2, no. 3, 2009, pages 992
SCHNELL: "Polymer Reviews", vol. 9, 1964, INTERSCIENCE PUBLISHERS, article "Chemistry and Physics of Polycarbonates"
U. GRIGO; K. KIRCHNER; P. R. MÜLLER: "Kunststoff-Handbuch, Band 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester", 1992, CARL HANSER VERLAG MÜNCHEN, article "Polycarbonate", pages: 117 - 299
U. MEIER-WESTHUES: "Polyurethane", 2007, VINCENTZ NETWORK, pages: 25 - 63

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104789104A (zh) * 2014-01-17 2015-07-22 佛山市顺德区博宜防腐涂料科技有限公司 高机械性能含羟基聚氨酯共聚丙烯酸水性工业漆
US10385152B2 (en) 2015-06-18 2019-08-20 Basf Se Copolymer made from cyclic exo-vinyl carbonate acrylates
WO2016202652A1 (fr) 2015-06-18 2016-12-22 Basf Se Copolymères composés d'exo-vinylène carbonatacrylates cycliques
US10570306B2 (en) 2015-07-30 2020-02-25 Basf Se Compositions containing polyanion, ethoxylated cationic polymer and phyllosilicates for improved oxygen barrier coatings
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
WO2018054609A1 (fr) 2016-09-21 2018-03-29 Henkel Ag & Co. Kgaa Composition à deux constituants à base de composés comportant au moins deux motifs exo-vinylène cyclocarbonate
US10604500B2 (en) 2016-09-21 2020-03-31 Basf Se Compounds having two or more exovinylene cyclocarbonate units
EP3363840A1 (fr) 2017-02-17 2018-08-22 Henkel AG & Co. KGaA Composition de polyuréthane à deux composants comprenant un catalyseur latent
WO2018149672A1 (fr) 2017-02-17 2018-08-23 Henkel Ag & Co. Kgaa Composition de polyuréthane à deux composants comprenant un catalyseur latent
WO2018162205A1 (fr) 2017-03-06 2018-09-13 Henkel Ag & Co. Kgaa Composition à un constituant à base de composés comportant au moins deux motifs exo-vinylène cyclocarbonate
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
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
WO2019219469A1 (fr) 2018-05-18 2019-11-21 Basf Se Monomères comprenant au moins une unité 4-(2-oxyéthylidène)-1,3-dioxolan-2-one et leur utilisation
US11613524B2 (en) 2018-05-18 2023-03-28 Basf Se Monomers comprising at least one 4-(2-oxyethylidene)-1,3-dioxolan-2-one unit and use thereof
CN110003753A (zh) * 2019-04-25 2019-07-12 哈尔滨工业大学无锡新材料研究院 一种用于双向拉伸聚酯薄膜的高阻隔涂料及其制备方法
CN113929867A (zh) * 2021-09-15 2022-01-14 深圳市力合科创股份有限公司 铸膜液及其制备方法、以及高阻隔复合膜及其制备方法
CN113929867B (zh) * 2021-09-15 2023-08-11 深圳市力合科创股份有限公司 铸膜液及其制备方法、以及高阻隔复合膜及其制备方法
CN115572530A (zh) * 2022-09-08 2023-01-06 浙江锦美材料科技有限公司 一种用于iml工艺的硬化涂层及其制备方法
CN115572530B (zh) * 2022-09-08 2023-08-15 锦美星灿新材料(安徽)有限公司 一种用于iml工艺的硬化涂层及其制备方法

Also Published As

Publication number Publication date
WO2012175427A3 (fr) 2013-04-04

Similar Documents

Publication Publication Date Title
WO2012175427A2 (fr) Production de films à couches barrières souples contenant des phyllosilicates
WO2012175431A2 (fr) Production de films dotés de revêtements barrières souples contenant des phyllosilicates
EP2113523B1 (fr) Systèmes de revêtement non agglomérants et durcissables par rayonnement à base de dispersions de polyuréthane hautement moléculaires aqueuses
EP2513178B1 (fr) Dispersions de polyuréthane-acrylate peu visqueuses
EP2396356B1 (fr) Systèmes de revêtement aqueux à base d'acrylates d'uréthane physiquement siccatifs
EP2218739B2 (fr) Systèmes de revêtement aqueux à base d'acrylate d'uréthane physique sec
EP1647399B1 (fr) Feuille plastique stratifiée, déformable, revêtue d' une peinture "soft touch" et structures plastiques stratifiées et leur méthode de production
EP3350243B1 (fr) Feuilles recouvertes presentant en particulier une haute resistance a l'hydrolyse et corps de formage fabrique a partir de celle-ci
EP2113527B1 (fr) Feuille déformable dotée d'un revêtement durcissable au rayonnement et corps de formage ainsi fabriqués
EP2178939B1 (fr) Procédé de production de systèmes de revêtements durs à base de dispersions aqueuses de polyuréthane
EP2542600B1 (fr) Dispersions aqueux de polyurethane
EP3283589B1 (fr) Procédé de fabrication de corps façonnés pourvus d'un revêtement durci par rayonnement
EP2460668B1 (fr) Document de sécurité et/ou de valeur doté d'une couche de revêtement équipée de manière à résister aux égratignures
WO2010091823A1 (fr) Film de support comprenant une couche de polyuréthane
EP2216352A1 (fr) Laque de polyuréthane 2K pour feuilles de support
DE102010010621A1 (de) Strahlenhärtbare Schlagschäume
WO2020081482A1 (fr) Résistance chimique améliorée dans des dispersions de polyuréthane par neutralisation avec une amine
EP3670556A1 (fr) Couche d'amorce aqueuse
JP2024025197A (ja) 化粧シート及び化粧材
WO2022037950A1 (fr) Systèmes d'agents de revêtement, constitués d'un revêtement de base et d'un revêtement supérieur, et produit semi-fini à base de ceux-ci et production associée
WO2013113739A1 (fr) Dispersions de faible viscosité de polyuréthane cationique hydrophilisé
EP2912079A1 (fr) Agent de revêtement destiné à des revêtements pouvant être dépolis

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12728508

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12728508

Country of ref document: EP

Kind code of ref document: A2