WO2020152292A1 - Papier barrière à pourcentage élevé de fibres de cellulose - Google Patents

Papier barrière à pourcentage élevé de fibres de cellulose Download PDF

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Publication number
WO2020152292A1
WO2020152292A1 PCT/EP2020/051669 EP2020051669W WO2020152292A1 WO 2020152292 A1 WO2020152292 A1 WO 2020152292A1 EP 2020051669 W EP2020051669 W EP 2020051669W WO 2020152292 A1 WO2020152292 A1 WO 2020152292A1
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WIPO (PCT)
Prior art keywords
barrier
paper
wax
oil
mass fraction
Prior art date
Application number
PCT/EP2020/051669
Other languages
German (de)
English (en)
Inventor
Nadia EL-KARZAZI
Dieter Becker
Original Assignee
Mitsubishi Hitec Paper Europe Gmbh
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Publication date
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Publication of WO2020152292A1 publication Critical patent/WO2020152292A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/18—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising waxes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/02—Material of vegetable origin
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper

Definitions

  • the present invention relates to a barrier paper comprising a paper substrate, the paper substrate comprising cellulose fibers and the mass fraction of the cellulose fibers being greater than or equal to 90%, and a barrier layer arranged on the front and / or rear side of the paper substrate, the barrier layer being a polymeric binder and at least one wax and / or comprises or from at least one vegetable oil.
  • the present invention also relates to a food packaging, preferably a food bag, made from a barrier paper according to the invention and the use of a barrier paper according to the invention as a food packaging.
  • the present invention further relates to a method for producing a barrier paper. Groceries, such as sausage, cheese or baked goods or frozen goods, are usually offered and handed over to customers for hygiene or freshness reasons in packaging.
  • a composite material is often used as a more fat-resistant alternative to sandwich paper.
  • a composite packaging material can, for example, consist of a composite material formed from a paper and a plastic and / or aluminum foil. If there is no polyethylene coating (PE), fluorocarbones can be used as water-repellent chemicals. For example, paper is coated on one side with polyethylene, often in an energy-intensive extrusion process, or with aluminum foil. These composite packaging materials are characterized by their high fat and moisture resistance. By selecting the appropriate polyethylene, composite packaging materials can be manufactured that are suitable for the storage of frozen food. If these composite packaging materials are used for paper recycling, however, these materials significantly interfere with the recycling process.
  • PE polyethylene coating
  • the composite packaging materials cannot be defibrated sufficiently during the recycling process and so-called wet-strength specks form.
  • Specks are remnants of the plastic or aluminum foil to which paper fibers still adhere. The necessary separation of the specks in the fiber processing process results in a not inconsiderable loss of fiber, which is withdrawn from the process. These specks have to be removed during the recycling process. It is also not possible to compost these composites because the plastic or aluminum foils used are not biodegradable.
  • DE 10 2014 119 572 A1 describes packaging paper for foods with a basis weight between 20 g / m 2 and 40 g / m 2 , and with a mass fraction of filler that is less than 20% based on the mass of the uncoated paper - points.
  • the packaging paper has a coating on at least one side, which comprises a vegetable oil, talcum and a binder encapsulated in a polymer.
  • a packaging always consists of different components, namely the packaging material and the packaging aid.
  • the goods that are packed are called packaged goods.
  • Packaging aids are materials that increase the strength of the packaging or are only possible make, such as nails, adhesive tapes, clips and strapping, which ensure the crate of boxes and boxes. Packing aids also include labels such as labels on beverage bottles, banderoles on cans and closures of bottles and glasses, labeling agents (e.g. warning labels), desiccants, securing agents (e.g. seals, seals) or upholstery agents (corner cushions, air cushions) etc.).
  • Packaging material is the name for the container in which the packaged goods (goods) are packed.
  • packaging box, box, crate, sack, can, bin, glass, bottle, canister, bag, shrink hood, etc.
  • Materials are referred to as packaging materials from which the packaging is formed.
  • packaging materials include, for example, wood, glass, metal, paper and plastic.
  • Cardboard is a term for packaging made of corrugated cardboard.
  • the object of the present invention is to provide a packaging material which can be fed to paper recycling without the recycling process being impaired by the formation of specks or other rejects, such as foils.
  • the packaging material should be designed so that it is suitable for contact with food and has a low water and water vapor permeability and a high fat resistance.
  • the packaging material should also be suitable for use as packaging for frozen materials.
  • it is necessary that the packaging material is sufficiently water-resistant so that the packaging does not tear when the packaging comes into contact with water (eg due to condensation on the outside or inside of the packaging, caused by the transport of the goods can occur to consumers).
  • the packaging material should preferably also be capable of being designed so that it does not tear during normal use.
  • a barrier paper comprising a) a paper substrate (11), having a front side and a rear side opposite the front side, the paper substrate comprising cellulose fibers and the mass fraction of the cellulose fibers being greater than or equal to 90%, based on the Total mass of the paper substrate and determined as the dry mass fraction, and b) a barrier layer (12) arranged on the front and / or rear side of the paper substrate, the barrier layer (12) comprising or consisting of i) a polymeric binder and ii) at least one wax and / or at least one (preferably encapsulated) vegetable oil.
  • barrier papers according to the invention have a low water and water vapor permeability as well as a high fat and water resistance.
  • the high cellulose fiber content enables the formation of chemical bonds (covalent bonds and / or hydrogen bonds) between the paper substrate and the barrier layer (here in particular the polymeric binder of the barrier layer) . It is believed that the high cellulose fiber content and the associated high cellulose content in the paper substrate make it possible to form a particularly large number of bonds, in particular with the OH groups of the cellulose. Our own investigations have shown that this effect is formed with a cellulose fiber content of greater than or equal to 90% and is further increased with increasing cellulose fiber content.
  • a barrier paper is therefore preferred according to the invention, the mass fraction of cellulose fibers being greater than or equal to 95.0%, preferably greater than or equal to 98%, particularly preferably being greater than 99%, based on the total mass of the paper substrate in the paper substrate and determined as the dry mass fraction.
  • Optimal is a cellulose fiber content of 99.9, 99.8, 99.7, 99.6, 99.5, 99.4, 99.3 or 99.2% and the paper substrate only contains small amounts of auxiliary materials required inorganic fillers, Starch, alum and / or glue.
  • a barrier paper is preferred according to the invention, the paper substrate containing only inorganic fillers, starch, alum and / or glue in addition to the cellulose fibers.
  • Our own studies have shown that papers with a low lignin content are particularly well suited for use as a paper substrate in barrier papers according to the invention.
  • lignin has a number of important tasks in the pulp fibers used for paper production.
  • Lignins are essential for the strength of the cellulose fibers. It is therefore surprising that paper substrates with a low lignin content lead to barrier papers with improved properties.
  • the natural lignin content in wood is - depending on the type of wood used - approx. 19 to 32%.
  • a barrier paper is preferred according to the invention, the mass fraction of lignin in the cellulose fibers being less than or equal to 5.0%, preferably being less than or equal to 4.5%, particularly preferably being less than or equal to 4.0%, based on the total mass of the cellulose fibers and determined as an oven-dry mass fraction.
  • Sulphate pulp fibers are particularly well suited for use in paper substrates in barrier papers according to the invention.
  • Sulphate pulp fibers are characterized by a low lignin content, since the lignin is washed out of the wood raw material during the sulphate process.
  • the cell walls of the wood raw material are opened and the lignin and polyoses contained in the plant material are separated.
  • the resulting sulfate pulp fibers usually have a lignin content of about 3 to 5% and are particularly suitable for use in paper substrates in barrier papers according to the invention.
  • a barrier paper is preferred according to the invention, the pulp fibers having a Kapp number, determined according to ISO 302: 2004, of less than or equal to 30, preferably less than or equal to 15, particularly preferably less than or equal to 7.
  • a barrier paper is preferred according to the invention, the mass fraction of sulfate pulp fibers being greater than or equal to 90.0%, preferably greater than or equal to 95.0%, particularly preferably greater than 99.5%, based on the total mass of the pulp fibers in the paper substrate and determined as oven-dry mass fraction.
  • a barrier paper in which all the cellulose fibers in the paper substrate are sulphate cellulose fibers is particularly preferred according to the invention.
  • fresh fibers also called primary fibers
  • recycled fibers made from recycled paper also called secondary fibers
  • mixtures of fresh fibers and recycled fibers can be used as cellulose fibers.
  • a fresh fiber is understood to mean a fiber which has been obtained directly from the vegetable starting material (mostly wood).
  • Recycled fibers consist of a fiber material that was previously used at least once in other paper or cardboard products, i.e. that was obtained from waste paper and / or cardboard. Our own studies have shown that a high proportion of fresh fibers has a positive effect on the barrier effect of the barrier paper according to the invention.
  • a barrier paper is therefore preferred according to the invention, the paper substrate comprising fresh fibers and the mass fraction of fresh fibers being greater than or equal to 80%, preferably greater than or equal to 90%, particularly preferably greater than or equal to 95%, based on the total mass of the cellulose fibers and determined as the dry mass fraction.
  • Particularly preferred according to the invention is a barrier paper in which all the cellulose fibers in the paper substrate are fresh fibers, i.e. where the mass fraction of fresh fibers is 100%, based on the total mass of the cellulose fibers and determined as a mass fraction of dry kilns.
  • a bleaching process of the cellulose fibers can have a negative effect on the properties of the resulting barrier paper according to the invention. Without wishing to be bound by any particular theory, it is believed that bleaching reduces the number of free OH groups that can form covalent and / or hydrogen bonds.
  • a barrier paper is preferred according to the invention, the cellulose fibers being unbleached.
  • a barrier paper is preferred according to the invention, the cellulose fibers being softwood, hardwood, straw cellulose fibers or mixtures thereof.
  • a barrier paper is preferred according to the invention, wherein the paper substrate has a basis weight of 32 to 100 g / m 2 , preferably 40 to 80 g / m 2 , particularly preferably 45 to 70 g / m 2 .
  • the paper substrate having a short-fiber cellulose with a Schopper-Riegler degree of at least 30 ° SR and a long-fiber cellulose with a Schopper-Riegler degree of at least 25 ° SR and with the paper substrate comprises at least a mass fraction of 50% short fiber pulp, based on the total mass of short fiber pulp and long fiber pulp.
  • the short-fiber pulp has a Schopper-Riegler degree of at least 35 ° SR, preferably of at least 39 ° SR and / or the long-fiber pulp has a Schopper-Riegler degree of at least 30 ° SR , preferably of at least 33 ° SR. It is preferred according to the invention if the paper substrate comprises a mass fraction of at least 70% short fiber pulp, preferably between 70 and 75% short fiber pulp, based on the total mass of short fiber pulp and long fiber pulp.
  • a barrier paper is preferred according to the invention, the wax being beeswax.
  • beeswax is a wax separated from honeybees (e.g. Apis mellificä), which is used by them to build the honeycombs.
  • Beeswax consists of myricine, a mixture of complex wax esters (approx. 70%) with myricylic palmitic acid as the main component, normal fatty acids, in particular cerotinic and melissic acid, hydroxy fatty acids (13-14%), hydrocarbons (10-14%) and other substances, such as bee-specific flavorings (6%).
  • beeswax has very good properties and is very suitable for use in barrier layers. It can also be used to manufacture barrier papers that are made from renewable raw materials and are biodegradable.
  • beeswax can be described using the main components, namely palmitic acid myricylester, cerotinic acid and melissic acid. According to the invention, preference is thus given to a barrier paper which comprises, in the barrier layer, myricylic palmitate, cerotic acid and / or melissic acid.
  • the beeswax can be natural beeswax (cera) or bleached beeswax (Cera alba). Our own studies have shown that the calibration process has no significant effects on the barrier effect of the barrier papers according to the invention produced with bleached beeswax, but the optical properties of the barrier paper can be adjusted.
  • a barrier paper is preferred according to the invention, the at least one wax being a wax based on a vegetable oil.
  • barrier papers according to the invention have a high resistance to fats and / or oils and / or moisture and can be produced entirely or predominantly from renewable raw materials if the wax is a wax based on a vegetable oil .
  • the use of a polymeric binder surprisingly forms the barrier layer in such a way that it does not detach from the paper substrate or that the wax is transferred to other objects or the food.
  • a wax based on a vegetable oil is understood to mean a wax that is obtained by chemical modification of a vegetable oil.
  • the chemical modification can be, for example, a partial or complete hydrogenation using a metallic catalyst, for example nickel, and hydrogen, all or part of the double bonds of the oil being hydrogenated to form single bonds.
  • the waxes are not liquid at 20 ° C, but solid. The chemical modification of the vegetable oil thus increases the melting point.
  • a vegetable oil is understood to mean a fatty acid triglyceride that is obtained from plants or parts of plants.
  • the oil is usually obtained by pressing, extracting or refining the oils from the plants or parts of plants. The extraction of the oils is known to the person skilled in the art. If plant seeds are used for oil production, these are referred to as oil seeds.
  • the oil occurs in the seeds in the form of lipids, which represent its cell membrane and energy reserves.
  • non-drying e.g. olive oil
  • semi-drying e.g. soybean or rapeseed oil
  • drying oils e.g. linseed or poppy seed oil.
  • drying means This does not mean evaporation, but the solidification of the oil due to the oxidation and polymerization of the unsaturated fatty acids.
  • semi-drying and drying oils as the starting material for producing the waxes used according to the invention is preferred.
  • Possible sources of vegetable oil are agai oil, algae oil, argan oil (from the fruits of the argan tree), avocado oil (from the flesh of the avocado of the avocado tree), babagu oil, cottonseed oil (from the seeds of the cotton plant), borage oil or borage seed oil (from the borage seeds) plant), cupuagu butter, cashew nut oil, safflower oil (also called “safflower oil", from the seeds of safflower or Carthamus), peanut oil (from the fruit of the peanut plant), hazelnut oil (from the hazelnuts of the hazelnut bush), hemp oil (from the Seeds of hemp), jatropha oil (from the seeds of Jatropha curcas), jojoba oil (actually a liquid wax; from the seeds of jojoba), camellia oil (from the seeds of Camellia oleifera, Camellia sinensis or Camellia japonica, cocoa butter, coconut oil (from the Seed meat of the coconut, the tree fruit of the coconut palm), pumpkin seed
  • the at least one wax based on a vegetable oil being a wax based on an oil, selected from the list comprising palm oil, coconut oil, poppy oil, olive oil, linseed oil, soybean oil, sunflower oil, safflower oil and rapeseed oil, preferably the wax based on a vegetable oil is a wax based on a soybean oil, i. H. about soybean oil wax or soy wax.
  • the waxes from the oils mentioned above as preferred have particularly good properties.
  • the waxes made from these oils are characterized by their high resistance and can be produced with high melting points.
  • the waxes used according to the invention namely palm oil wax, coconut oil wax, poppy oil wax, olive oil wax, linseed oil wax, soybean oil wax, sunflower oil wax, safflower oil wax and rapeseed oil wax, show a significant increase in the resistance to fats and / or oils and / or moisture when used in barrier papers according to the invention.
  • the use of soybean oil wax is particularly preferred according to the invention. Our own studies have shown that the use of soybean oil wax, in addition to its resistance to fat, oil and moisture, can also result in very low water vapor permeability. Soybean oil wax also has the advantage that it can be made tasteless and odorless.
  • Barrier papers are preferred according to the invention, the wax (in particular the wax based on a vegetable oil) having a melting point above 40 ° C., preferably above 50 ° C., particularly preferably above 60 ° C.
  • the wax in particular the wax based on a vegetable oil
  • Our own studies have shown that very good results can already be obtained when using waxes with a melting point above 20 ° C.
  • the use of waxes with a melting point above 40 ° C can increase the resistance of the barrier papers to mechanical stress. This resistance is further increased with even higher melting points of the waxes.
  • Our own studies have also shown that the optimal melting point of the waxes is in the range of 60 to 80 ° C, provided the barrier papers are at temperatures between 6 ° C and 30 ° C should be used. If the barrier papers are also to be used at higher temperatures, it may make sense to use a wax with a higher melting point.
  • barrier papers are preferred, the mass fraction of the wax or waxes in the barrier layer being 6 to 98%, preferably 20 to 90%, particularly preferably 50 to 89%, very particularly preferably 50 to 78%, based on the total mass of the barrier layer.
  • Barrier papers are particularly preferred according to the invention, the mass fraction of the wax or waxes in the barrier layer being 20 to 78%.
  • a barrier paper is preferred according to the invention, the wax being carnauba wax.
  • a barrier paper which has at least one vegetable oil in the barrier layer instead of the at least one wax or in addition to the at least one wax.
  • a barrier paper is preferred according to the invention, the vegetable oil being an oil, but not, for example, not finally selected from the list comprising palm oil, coconut oil, poppy oil, olive oil, linseed oil, soybean oil, sunflower oil, safflower oil and rapeseed oil or a mixture thereof, preferably
  • the vegetable oil is sunflower oil, soybean oil, palm oil or rapeseed oil.
  • the at least one wax and / or the at least one vegetable oil is preferably at least partially covered with a polymer, particularly preferably the wax and / or the vegetable oil is encased in a polymer.
  • partial covers and / or shells which are also referred to as core-shell particles, can be produced, for example, by the method described in EP 2 046 492 B1.
  • the polymer is a copolymer of styrene and maleic anhydride derivatives.
  • the polymer preferably contains a maleimide group and is preferably formed by a copolymer with maleimide groups, in particular a copolymer of styrene and maleic anhydride derivatives.
  • partial covers and / or shells which are also referred to as core-shell particles, can alternatively be produced, for example, using the method described in EP 2 545 102 B1.
  • the polymer contains a cyclic imide which contains polymer which is a reaction product of a reaction imidization of a copolymer of a cyclic anhydride with a vinyl monomer and a cyclic anhydride (CA) content between 22 and 50 Mol% has, with an ammonium (NH3) solution in a CA: NH3 ratio between 1.4: 1 and 1: 1.2 at elevated temperature until at least 50% of the CA is imidized in the imide.
  • a cyclic imide which contains polymer which is a reaction product of a reaction imidization of a copolymer of a cyclic anhydride with a vinyl monomer and a cyclic anhydride (CA) content between 22 and 50 Mol% has, with an ammonium (NH3) solution in a CA: NH3 ratio between 1.4: 1 and 1: 1.2 at elevated temperature until at least 50% of the CA is imidized in the imide.
  • the polymer containing a cyclic imide is the reaction product of an indimitation reaction of a polystyrene-maleic anhydride which has a maleic anhydride (MA) content between 22 and 34 mol%, with an ammonium ( NH3) solution in an MA: NH3 ratio between 1.4: 1 and 1: 1.2 at elevated temperature until at least 50% of the MA is imidized in maleimide, which is said to further characterized said cyclic imide-containing polymer to have a particle size between and approximately 25-150 nm; a solid mass fraction between and in about 25 and 45%; and has a pH between 6.0 and 9.0.
  • MA maleic anhydride
  • NH3 ammonium
  • the aforementioned imidization reaction is carried out in the presence of a non-water-soluble product, such as, for example, at least one vegetable oil and / or at least one wax;
  • a non-water-soluble product such as, for example, at least one vegetable oil and / or at least one wax
  • All binders customary in paper production are suitable as polymeric binders.
  • the polymeric binder is a crosslinked or uncrosslinked binder selected from the group consisting of starch, polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, ethylene-vinyl alcohol copolymer, a combination of polyvinyl alcohol and ethylene-vinyl alcohol copolymer, ethylene Vinyl acetate copolymer, silanol group-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, modified polyethylene glycol, unmodified polyethylene glycol, a-isodecyl-cj-hydroxy-poly (oxy-1, 2-ethanediyl), styrene-butadiene latex, styrene-acrylate polymers , Acrylic copolymers and mixtures thereof.
  • barrier papers according to the invention have a particularly high resistance to fat, oil and moisture if the polymeric binder is one or more styrene-acrylate polymers or acrylate polymers or if the binder comprises them.
  • ethylene-vinyl alcohol copolymer and polyvinyl alcohol are the least preferred.
  • Barrier papers according to the invention are therefore particularly preferred if they do not contain ethylene-vinyl alcohol copolymer and / or polyvinyl alcohol in the barrier layer.
  • the styrene-acrylate polymer or acrylate polymer produces a copolymer using two, three, four, five, six or all of the monomers selected from the group consisting of methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate and styrene.
  • the barrier layer does not comprise polyethylene (PE).
  • the mass fraction of the polymeric binder in the barrier layer is 94 to 2%, preferably 80 to 10%, particularly preferably 50 to 11%, based on the total mass of the barrier layer.
  • the mass fraction of the polymeric binder in the barrier layer is 94 to 2% and that the mass fraction of the wax in the barrier layer is 6 to 98% and it is even more preferred if the mass fraction of the polymeric binder in the barrier layer Is 80 to 10% and the mass fraction of the wax in the barrier layer is 80 to 90% and it is even more preferred if the mass fraction of the polymeric binder in the barrier layer is 50 to 11% and that the mass fraction of the wax in the barrier layer Is 50 to 89%.
  • the mass fraction of the wax, which in this embodiment is preferably beeswax, in the barrier layer is particularly preferred if the mass fraction of the wax, which in this embodiment is preferably beeswax, in the barrier layer
  • A) is at least 6%, preferably at least 10%, more preferably at least 15%, more preferably at least 17% and / or
  • B) is at most 45%, preferably at most 40%, more preferably at most 35%, more preferably at most 30%.
  • the mass fraction of the wax, which in this embodiment is preferably beeswax, in the barrier layer is 6 to 45%, preferably 10 to 40%, more preferably 15 to Is 35%, more preferably 17 to 30%.
  • barrier papers are preferred in which the mass per unit area of the barrier layer is in the range from 1.5 to 8 g / m 2 , preferably in the range from 2.0 to 5.5 g / m 2 , particularly preferably in the range from 3.0 up to 5.0 g / m 2 .
  • barrier papers with the low area-related masses specified here have very good resistance to grease, oil and moisture.
  • the durability can easily be improved by increasing the mass per unit area, the improvement is only minimal, so that the increased material consumption does not justify the slight improvement.
  • a mass per unit area of less than 1.5 g / m 2 the resistance of the pure carrier substrate is also improved, but the resistance is not always sufficient for some areas of application (e.g. very fatty and moist foods).
  • Our own studies have shown that optimum resistance can be obtained if the mass per unit area of the barrier layer is in the range from 3.0 to 5.0 g / m 2 .
  • the polymeric binder consists of two or more binders and at least one binder is an anionic binder.
  • An anionic binder is understood to mean a binder which contains several negative charges which are stabilized by cations (for example metal cations or ammonium).
  • a polymeric binder is understood to mean a binder which has been built up from a large number of molecules by polycondensation and in which one type or more types of atoms or atom groups (so-called repeating units) are repeatedly strung together and the number of repeat units per molecule is more than 25.
  • the glass transition temperature of the anionic binder determined on the basis of dynamic differential calorimetry (DSC) is less than or equal to 120 ° C.
  • DSC dynamic differential calorimetry
  • anionic binder is a copolymer.
  • Suitable anionic binders are, for example, partially or completely deprotonated polyacrylic acid (or copolymers thereof, for example with acrylic esters), partially or completely deprotonated polymethacrylic acid (or copolymers thereof, for example with methacrylic esters), copolymers of polyacrylic acid esters (preferably methyl or ethyl esters), copolymers of Polymethacrylic acid esters (preferably methyl or ethyl esters) or polyacrylamides or copolymers thereof.
  • the barrier layer (12) additionally comprises a wax based on saturated hydrocarbons.
  • Barrier papers are preferred according to the invention, the wax based on saturated hydrocarbons having a melting point above 40 ° C., preferably above 50 ° C., particularly preferably above 60 ° C.
  • Barrier papers are preferred according to the invention, the wax based on saturated hydrocarbons containing one, two, three or more than three alkanes or consisting thereof selected from the group consisting of heneicosane, docosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane , Triacontane, hentriacontane, Dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, heptatriacontane, octatriacontane and nonatriacontane, preferably selected from the group consisting of hexacosane, heptacosane, octacosane, nonaco
  • the acrylate copolymer in the barrier layer is particularly preferably a copolymer with an average molar mass in the range from 50,000 to 150,000 g / mol, preferably in the range from 80,000 to 130,000 g / mol, particularly preferably in the range from 90,000 to 100,000 g / mol.
  • the average molar mass is determined with the aid of gel permeation chromatography (GPC) with tetrahydrofuran (THF; tetramethylene oxide; 1,4-epoxybutane; oxacyclopentane) as a solvent, polystyrene as standard and detection using an RI detector (refractive index detector).
  • GPC gel permeation chromatography
  • the acrylate copolymer in the barrier layer is particularly preferably a copolymer produced using two, three, four, five, six or all monomers selected from the group consisting of methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid -2-ethylhexyl ester, 2-ethylhexyl methacrylic acid and styrene.
  • the properties of the resulting acrylate copolymer can be optimized by selecting the monomers used to produce the acrylate copolymer.
  • Surveys of our own have surprisingly shown that an acrylate copolymer which has been prepared from methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and 2-ethylhexyl methacrylate and / or styrene has particularly good barrier properties.
  • the acrylate copolymer is particularly preferably a random copolymer
  • a barrier paper is preferred according to the invention if the binder in the barrier layer comprises or consists of one or more acrylate copolymers and / or styrene-acrylate polymers.
  • a barrier paper is particularly preferred according to the invention if the binder in the barrier layer comprises or consists of one or more acrylate copolymers and / or styrene-acrylate polymers and the wax is a beeswax. It is further preferred here if the binder comprises or consists of one or more styrene-acrylate polymers and the wax is a beeswax.
  • a mixture of one or more acrylate copolymers and / or styrene-acrylate polymers and beeswax is applied during the production of the barrier paper according to the invention and the barrier layer is formed therefrom. It is preferred according to the invention if this mixture has a pH in the range from 8 to 11 and / or a Brookfield viscosity (speed 60 / min and spindle no. 2) in the range from 80 to 300 cP.
  • Barrier papers according to the invention in which the mixture of an acrylate copolymer (in particular styrene-acrylate polymer) and beeswax have bands in the IR spectrum at 1601, 1549, 1493, 760 and 698 cm-1 ( ⁇ 10 cm-1) are particularly preferred .
  • a barrier paper is preferred according to the invention, the barrier paper additionally containing an intermediate layer (13) and the intermediate layer (13) being arranged between the paper substrate and the barrier layer. It has been shown in our own investigations that the properties of the resulting barrier paper are particularly good if the barrier layer is not applied directly to the base paper as a paper substrate, but an intermediate layer is first applied to the paper substrate.
  • the intermediate layer (13) contains a pigment.
  • a barrier paper is preferred according to the invention if the pigment is an organic pigment, inorganic pigment or a mixture of organic pigments and inorganic pigments.
  • a barrier paper is preferred according to the invention if the pigment is an inorganic pigment selected from the list consisting of calcined kaolin, kaolin, kaolinite, magnesium silicate hydrate, silicon oxide, bentonite, calcium carbonate, aluminum hydroxide, aluminum oxide and boehmite.
  • the pigment is in platelet form, preferably with an aspect ratio of 5 to 100, preferably from 15 to 100, more preferably from 20 to 80.
  • the aspect ratio is Quotients between the diameter and the thickness of the flake of the pigment before mixing with the other components.
  • An aspect ratio of 20 means that the diameter of the plate is 20 times larger than the thickness of the plate.
  • kaolin, kaolinite and talc are platelet-shaped and are therefore particularly preferred as pigments.
  • a barrier paper is preferred according to the invention if the mass fraction of the pigment in the intermediate layer is 5 to 60%, preferably 15 to 40%, particularly preferably 20 to 40%, based on the total mass of the intermediate layer.
  • a barrier paper is preferred according to the invention if the intermediate layer contains a binder and the binder is preferably a crosslinked or undamaged binder selected from the group consisting of starch, polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, ethylene-vinyl alcohol copolymer , a combination of polyvinyl alcohol and ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, silanol group-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, acrylate copolymer, modified polyethylene glycol, unmodified polyethylene glycol, a-isodecyl-u) -hydroxy-poly (oxy-1,2-ethanediyl), styrene-butadiene latex, styrene-acrylate polymers, film-forming acrylic copolymers and mixtures thereof.
  • the binder is preferably a crosslinked or undamaged binder selected from the group
  • a barrier paper is preferred according to the invention if the binder comprises or consists of one or more acrylate copolymers and / or styrene-acrylate polymers.
  • a barrier paper is particularly preferred according to the invention if the binder comprises or consists of one or more acrylate copolymers and / or styrene-acrylate polymers and the wax is a beeswax. It is further preferred here if the binder comprises or consists of one or more styrene-acrylate polymers and the wax is a beeswax.
  • a mixture of one or more acrylate copolymers and / or styrene-acrylate polymers and beeswax is applied during the production of the barrier paper according to the invention. It is preferred according to the invention if this mixture has a pH in the range from 8 to 11 and / or a Brookfield viscosity (speed 60 / min and spindle no. 2) in the range from 80 to 300 cP. Particularly preferred are barrier papers according to the invention in which the mixture of an acrylate copolymer (in particular styrene-acrylate polymer) and beeswax bands in the IR spectrum at 1601, 1549, 1493, 760 and 698 cnr 1 ( ⁇ 10 cm 1 ).
  • a barrier paper is preferred according to the invention if the mass fraction of the binder in the intermediate layer is 95 to 40%, preferably 85 to 60%, particularly preferably 80 to 60%, based on the total mass of the intermediate layer.
  • Barrier papers are preferred according to the invention, the mass per unit area of the intermediate layer being in the range from 1.5 to 6 g / m 2 , preferably in the range from 2.0 to 5.5 g / m 2 , particularly preferably in the range from 2.0 up to 4.8 g / m 2 .
  • a barrier paper is preferred according to the invention, the intermediate layer additionally comprising a wax based on saturated hydrocarbons.
  • a barrier paper is preferred according to the invention, the wax based on saturated hydrocarbons in the intermediate layer having a melting point above 40 ° C., preferably above 50 ° C., particularly preferably above 60 ° C.
  • a barrier paper is preferred according to the invention, the wax based on saturated hydrocarbons in the intermediate layer containing one, two, three or more than three alkanes or consisting of selected from the group consisting of heneicosane, docosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, Octacosan, Nonacosan, Triacontan, Hentriacontan, Dotriacontan, Tritriacontan, Tetratriacontan, Pentatriacontan, Hexatriacontan, Heptatriacontan, Octatriacontan and Nonatriacontan.
  • a barrier paper according to the invention is preferred, the backing paper having further layers on the back.
  • the back can be coated with a starch layer, preferably modified starch, particularly preferably modified corn starch.
  • the properties of the barrier paper can be improved by a back coating. For example, it is thus possible to ensure that the barrier paper can be printed on the back.
  • the barrier paper has a Bekk smoothness, determined on the basis of ISO 5627, in the range from 100 to 1200 s on one or both sides. It is preferred if the barrier layer has a Bekk smoothness in the range from 100 to 1200 s, provided that the barrier layer is an outer layer. In contrast to ISO 5627, the Bekk smoothness is not determined on both sides of the barrier paper in this case, but only on the barrier layer of the barrier paper.
  • a barrier paper is preferred according to the invention if the barrier paper has a water vapor permeability according to DIN 53122-1 of less than or equal to 300 g / (m 2 d), preferably less than or equal to 250 g / (m 2 d), particularly preferably of less than or equal to 150 g / ( m 2 d).
  • the barrier paper according to the invention not only has a very high resistance to fat, but also a low water vapor permeability.
  • a low water vapor permeability in packaging is desirable for food, since the packaged food does not dry out prematurely and remains fresh for longer.
  • barrier paper is preferred according to the invention if the barrier paper has a KIT value of at least 5, preferably at least 8, particularly preferably at least 12; measured using the Tappi 559 method.
  • barrier papers according to the invention can have a KIT value of more than 12 and thus show excellent bed resistance, which is in the same range as the fat resistance of barrier papers coated with plastic or aluminum foil.
  • a barrier paper is preferred according to the invention if the barrier paper has a fat permeability with turpentine oil according to Tappi 454 of at least 1300 s, preferably of at least 1500 s, particularly preferably of at least 1800 s.
  • a barrier paper is preferred according to the invention, the barrier paper having a fat permeability of at least level 5, preferably of at least level 3, particularly preferably of at least level 1; measured according to method DIN 53116.
  • a barrier paper is preferred according to the invention if the mass per unit area of that of the barrier paper is in the range from 33 to 120 g / m 2 , preferably in the range from 35 to 80 g / m 2 , particularly preferably in the range from 40 to 50 g / m 2 lies.
  • a barrier paper is preferred according to the invention, the binder comprising or consisting of one or more acrylate copolymers and / or styrene-acrylate polymers and the wax being a beeswax and the mass fraction of beeswax in the barrier layer being 6 to 45% , preferably 10 to 40%, more preferably 15 to 35%, more preferably 17 to 30% and the mass fraction, based on the total mass of the cellulose fibers in the paper substrate, of sulphate cellulose fibers being greater than or equal to 90.0% .
  • a barrier paper is preferred for use as wrapping paper, underlay paper, intermediate and / or release paper for food, preferably for packaging baked goods, sandwiches, bread, burgers, meat products, fish, sausages and / or cheese.
  • the paper substrate is coated with the barrier layer both on the front side and on the rear side, an intermediate layer preferably being arranged between the barrier layers and the paper substrate.
  • an intermediate layer preferably being arranged between the barrier layers and the paper substrate.
  • the barrier papers according to the invention not only have excellent resistance to fats and / or oils and / or moisture, but also a barrier or Have a barrier effect against mineral oils.
  • Mineral oils often occur in recycled paper paper or cardboard that is not intended for the direct packaging of food. However, if they come into contact with food, for example if food is sent in a box, it cannot be ruled out that mineral oils will pass on to the food, even if the food is packed in separate packaging. For example, mineral oil residues have been found in chocolate from advent calendars in the past, which were absorbed by the chocolate through the contact of the chocolate with the cardboard packaging.
  • Barrier papers according to the invention are surprisingly characterized in that they not only prevent the fat, oil and moisture of the food from escaping to the outside, but also protect the food packaged with it from contamination with mineral oils.
  • packaging cartons from the barrier papers according to the invention which have the barrier layer in the interior of the packaging carton.
  • inner bag packaging from barrier papers according to the invention.
  • Another aspect of the present invention relates to a food packaging, preferably a food bag, made from a barrier paper according to the invention.
  • barrier paper as a food bag, wrapping paper, underlay paper, interleaving and / or separating paper for foodstuffs, preferably for wrapping, underlaying, interposing and / or separating baked goods, fried and / or fried goods, snacks, sandwiches, bread, burgers, meat products, fish products, sausages and / or cheese.
  • a further aspect of the present invention relates to methods for producing a barrier paper (10), preferably a barrier paper according to the invention, comprising the following steps
  • Fig. 1 shows a barrier paper 10, which consists of a paper substrate 11 and a barrier layer 12.
  • the paper substrate has a front side and a rear side opposite the front side and comprises cellulose fibers, the mass fraction of the cellulose fibers being 99.9%, based on the total mass of the paper substrate.
  • a barrier layer 12 is arranged, which consists of a polymeric binder and a wax.
  • Fig. 2 shows a barrier paper 10, which consists of a paper substrate 1 1, an intermediate layer 13 and a barrier layer 12.
  • the paper substrate has a front side and a rear side opposite the front side and comprises cellulose fibers, the mass fraction of the cellulose fibers being greater than or equal to 99.9%, based on the total mass of the paper substrate.
  • the intermediate layer 13 is arranged on the front of the paper substrate 11.
  • the barrier layer 12, which consists of a polymeric binder and a wax, is in turn arranged on the intermediate layer 13.
  • the intermediate layer 13 preferably contains a pigment and a bin
  • Fig. 3 shows a barrier paper 10, which consists of a paper substrate 11 and two barrier layers 12.
  • the paper substrate has a front side and a rear side opposite the front side and comprises cellulose fibers, the mass fraction of the cellulose fibers being greater than or equal to 90%, based on the total mass of the paper substrate.
  • FIG. 4 shows a barrier paper 10, which consists of a paper substrate 11, two intermediate layers 13 and two barrier layers 12.
  • the paper substrate has a front side and a back side opposite the front side and comprises cellulose fibers, the mass fraction of the cellulose fibers being greater than or equal to 90%, based on the total mass of the paper substrate.
  • An intermediate layer 13 is arranged both on the front and on the back of the paper substrate 11.
  • a barrier layer 12 which consists of a polymeric binder and a wax.
  • the intermediate layers preferably contain a pigment and a binder.
  • a backing paper was used which was produced from sulfate pulp fibers on a paper machine into a paper web provided with starch sizing with a mass per unit area of 70 g / m 2 .
  • the mass fraction of the cellulose fibers is approximately 99.9%, based on the total mass of the paper substrate.
  • the paper substrate produced was calendered at a line load of 80 kN / m and a temperature of 80 ° C.
  • an intermediate coat which was in the form of an aqueous dispersion, was applied to the backing paper produced and this intermediate coat was then dried using IR and air drying, so that an intermediate layer with a basis weight of 3 g / m 2 resulted.
  • the composition of the intermediate coat (without taking water into account) is given in Table 1.
  • a barrier screed which was in the form of an aqueous dispersion, was applied to the intermediate layer and this barrier screed was then dried using IR and air drying, so that a barrier layer with a basis weight of 4 g / m 2 resulted.
  • the composition of the barrier screed (without taking water into account) is given in Table 1.
  • the resulting barrier paper which could be heat-sealed at 90, 120 and 150 ° C, had a weight per unit area of 77 g / m 2 and was measured for its properties.
  • Table 1 The results are summarized in Table 2.
  • Example 1 was repeated using a barrier screed (without consideration of water), the composition of which is given in Table 3.
  • the resulting barrier paper which could be heat-sealed at 90, 120 and 150 ° C, had a weight per unit area of 77 g / m 2 and was measured for its properties.
  • the results are summarized in Table 4.
  • Example 1 was repeated using a barrier screed (without consideration of water), the composition of which is given in Table 5.
  • Table 5 the composition of which is given in Table 5.
  • the resulting barrier paper which could be heat-sealed at 90, 120 and 150 ° C, had a weight per unit area of 77 g / m 2 and was measured for its properties. The results are summarized in Table 6. Table 6:

Abstract

La présente invention concerne un papier barrière (10) comprenant : a) un substrat en papier (11), présentant une face avant et une face arrière opposée à la face avant, le substrat en papier comprenant des fibres de cellulose et la fraction massique des fibres de cellulose étant supérieure ou égale à 90 %, rapportée à la masse totale du substrat en papier et déterminée en tant que fraction massique séchée à l'étuve, et b) une couche barrière (12) disposée face avant et/ou face arrière du substrat en papier, la couche barrière (12) comprenant un liant polymère et au moins une cire et/ou au moins une huile végétale ou étant constituée de ceux-ci. La présente invention concerne en outre un emballage alimentaire, de préférence des sachets alimentaires, fabriqués à partir d'un papier barrière selon l'invention et l'utilisation d'un papier barrière selon l'invention comme emballage alimentaire. La présente invention concerne en outre un procédé pour fabriquer un papier barrière.
PCT/EP2020/051669 2019-01-23 2020-01-23 Papier barrière à pourcentage élevé de fibres de cellulose WO2020152292A1 (fr)

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DE102019101670.3A DE102019101670A1 (de) 2019-01-23 2019-01-23 Barrierepapier mit hohem Zellstofffaseranteil
DE102019101670.3 2019-01-23

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WO2024067927A1 (fr) 2022-09-30 2024-04-04 Koehler Innovation & Technology Gmbh Composites à base biologique utilisés en tant que barrière contre la vapeur d'eau sur du papier

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WO2013075918A1 (fr) * 2011-11-22 2013-05-30 Unilever N.V. Matériau d'emballage revêtu
EP2545102B1 (fr) 2010-03-09 2014-12-31 Topchim N.V. Substrat thermoscellable et son procédé de fabrication
DE102014119572A1 (de) 2014-12-23 2016-06-23 Delfortgroup Ag Umweltfreundliches Verpackungspapier für Lebensmittel
EP3342929A1 (fr) * 2016-12-30 2018-07-04 Mitsubishi HiTec Paper Europe GmbH Papier barrière
WO2019121733A1 (fr) * 2017-12-22 2019-06-27 Mitsubishi Hitec Paper Europe Gmbh Papier barrière recyclable
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EP2046492B1 (fr) 2006-07-31 2012-06-06 Topchim N.V. Particule sous forme de gouttelette encapsulée et procédé de fabrication d'une telle particule
EP2545102B1 (fr) 2010-03-09 2014-12-31 Topchim N.V. Substrat thermoscellable et son procédé de fabrication
WO2013075918A1 (fr) * 2011-11-22 2013-05-30 Unilever N.V. Matériau d'emballage revêtu
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WO2016102094A1 (fr) * 2014-12-23 2016-06-30 Delfortgroup Ag Papier d'emballage écologique pour denrées alimentaires
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Publication number Priority date Publication date Assignee Title
WO2024067927A1 (fr) 2022-09-30 2024-04-04 Koehler Innovation & Technology Gmbh Composites à base biologique utilisés en tant que barrière contre la vapeur d'eau sur du papier
DE102022210442A1 (de) 2022-09-30 2024-04-04 Koehler Innovation & Technology Gmbh Bio-basierte Komposite als Wasserdampfbarriere auf Papier

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