TR201815930T4 - Paper or cardboard packages with barrier coating. - Google Patents

Abstract

The invention is a paper or cardboard package of mineral oil-resistant, recyclable paper having a barrier layer, a copolymer which can be produced by emulsion polymerization from C1 to C4 alkyl (meth) acrylates, acid monomers and optionally acrylic nitrile and other monomers. An aqueous polymer dispersion comprising the dispersion.

Description

DESCRIPTION PAPER OR CARDBOARD PACKAGING WITH BARRIER COATING The present invention is a mineral oil resistant, recyclable material having a barrier layer. A paper or cardboard package consisting of recyclable paper, C1 to C4 alkyl(meth)acrylates, acid monomers and optionally acryl nitrile and other containing a copolymer that can be produced from monomers by emulsion polymerization can be produced by applying an aqueous polymer dispersion, in which The glass transition temperature of the copolymer is between + 10 “C to + 45 °C. Barrier tab back packaging may be found on one of the surfaces of a multilayer packaging may form one of its layers.

Cardboard packages are normally produced from recycled paper. printed paper, Recycled paper known for newspaper printing, especially in the case of newsprint May contain mineral oil residues from printing inks used in this way. Even at room temperature this the volatile part of the residue evaporates and in the case of food packaging, it is put into the box. in packaged foodstuffs, for example on pasta, bulgur, rice or cornflakes they precipitate on. Most inner bags of polymer foils used today are also sufficient here. does not offer protection. In the researches of the Zürich Cantonal Laboratory, again In foodstuffs packaged in recycled paper packages mineral oil residues were detected in significant amounts. In volatile mineral oil compositions mainly harmful to health paraffin and naphthene type hydrocarbons and aromatic hydrocarbons, particularly those having 15 to 25 carbon atoms.

Therefore, there is a risk of contamination of foodstuffs with mineral oil residues. There is a need to reduce For packaging of foodstuffs the possibility of dispensing with the recycling of newsprint in the production of cardboard are available. This is undesirable for ecological reasons and new celluloses are not sufficient. It cannot be applied because it is not ready for use in large quantities. In another solution, is the abandonment of mineral oils in printing dyes for newspaper printing. This is technological gets caught in obstacles, especially in terms of the wiping strength of the print on the paper surface. obstacle exists. Barrier coatings against oils and fats in the packaging area compositions are described. Polymers 'Properties of good barrier against oily substrates' However, in this way, they have a good barrier effect against substances passing in gaseous form. It has been seen that mutlara does not necessarily exist, because the substances mentioned here are different. transport mechanisms are involved. In solid and liquid oils, transport over the fibers occurs, in which capillary forces and surface moistening play a role.

Capillary effect and humidification do not play a role in the problems in gaseous substances, instead, sorption, diffusion and porosity play important roles. Moreover The solid and liquid oils of hydrocarbons are also different, that is, the mineral oil components themselves they differ by their polarity and thus their diffusion behavior from the barrier layers.

The aim of the present invention is to use recycled paper contaminated with mineral oil. Although there is a risk of contamination of the packaging material with the components of volatile mineral oil. is the reduction.

According to the invention, this purpose is achieved by means of a packaging made of paper or cardboard, The packaging inside is at least partially contaminated with mineral oil recycled It is made of paper and inside the packaging, emulsion polymerization an aqueous polymer dispersion containing at least one copolymer that can be produced by comprising at least one barrier layer that can be produced by applying (a) one or more acyls selected from the group consisting of C1- to C4-Alkyl(meth)acrylates monomers (b) one or more acid monomers selected, for example, from Acryl acid and Methacrylic acid 0.1 to 5% by weight, (c) O-20% by weight Acryl nitrile and (d) 0 to 10% by weight of other monomers other than monomers (8) to (c), The glass transition temperature of the copolymer is between + 10 °C and + 45 °C. wherein the copolymer is constructed from at least 70% by weight acyl monomers (a), and wherein the barrier layer may be on at least one of the packaging surfaces or Also, the barrier layer is at least one of several layers of a multilayer packaging coating. can form the iris. The packaging is particularly suitable for foodstuffs.

The meaning of the term “contaminated with mineral oil” is determined by known analysis methods of the paper. contain volatile hydrocarbons, especially volatile paraffins, volatile naphthenes and/or volatile aromatic hydrocarbons having up to 25 carbon atoms.

Volatile hydrocarbons have up to 25 carbon atoms, for example 5 to 22 carbon atoms. those with atoms. As an application of the invention, mineral oil contamination suppression comes from volatile paraffins, volatile naphthenes and/or volatile aromatic contains hydrocarbons.

Below is the short spelling for "(Meth)acryl..." and similar definitions "Acryl or methacryl..." used as.

In the polymer dispersions used according to the invention, the polymers in the aqueous medium dispersions are present. Here, for example, completely desalinated water or water and from solvents that can be mixed with it, for example methanol, ethanol or tetrahydrofuran mixtures may occur. Preferably, organic solvents are not used.

The solids content of the dispersions is preferably from 15 to 75% by weight, preferably from 40% by weight to 60 is particularly preferably greater than 50% by weight. Solid content e.g. emulsion Appropriate adjustment of the amount of water and/or the amount of monomer used in the polymerization can be adjusted by of the polymer particles dispersed in the aqueous dispersion. The average particle size is preferably less than 400 nm, particularly less than 300 nm. between nm. Here, the particle size distribution is the mean particle size. The dso- value is understood, ie 50% by weight of the total mass of all particles is less than the dso- value have a smaller particle diameter. The particle size distribution is known as analytical The pH of the polymer dispersion is preferably greater than 4, in particular 5 to 9 It is adjusted to a pH value between

The copolymers used according to the invention are emulsions of radically polymerizable monomers. They are emulsion polymers that can be produced by polymerization. Copolymer, C1- to C4- (a) of one or more acyl monomers selected from the group consisting of alkyl(meth)acrylates is created. The acyl monomers (23) are preferably at least at least relative to the sum of all monomers. they are used. Especially preferred acyl monomers (a), Methylacrylate, Methylmethacrylate, Ethylacrylate and n-Butylacrylate.

The copolymer is formed from one or more acid monomers (b). Acid monomers ethylenic unsaturated, radically polymerizable monomers that contain at least one acid group contain, for example, those with carbon acid, sulfonic acid or phosphonic acid groups are monomers. Carbon acid groups are preferred. For example, Acryl acid, Methacrylic acid, Itacon acid, Maleic acid or Fumaric acid is in question. Preferably acid monomers (b) Acryl acid and They were selected from methacrylic acid. Acid monomers (b), by weight based on the sum of all monomers Copolymer optionally as other monomer (0), based on the sum of all monomers May be formed from 0 to 20% by weight Acrylnitrile. Find an app 1 - 20% by weight of copolymer, preferably 2 - 20% by weight of Acrylnitrile is created.

The copolymer may optionally be made from other monomers other than monomers (a) to (0) (d) can be created. The amount of other monomers (d) is here relative to the sum of all monomers 0 to 10% by weight or 0 to 5% by weight. 0.1 to 10% by weight in one application or 0.1 to 5% by weight of other monomers (d) are used. In another application form (a) to (0) other monomers different from the monomers are used.

Other monomers (d) are carbon containing up to 20 carbon atoms from C5-Cgo-Alkyl(meth)acrylates vinyl esters of acids, vinyl aromates having up to 20 carbon atoms, other than acryl nitrile ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing 1 to 10 carbon atoms, Aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two pairs of these monomers may be selected from the group consisting of bonds or monomers. For example, a Cs-Cio-Alkyl residue (Meth)acryl acidalkylester having, for example, 2-Ethylhexyl-acrylate. Especially Mixtures of (meth)acryl acid alkylester are also suitable. carbon having 1 to 20 carbon atoms vinyl ester of acids eg Vinyl Iaurate, Vinyl stearate, Vinyl propionate, Versatic acid vinyl ester and It is vinyl acetate. As vinyl aromatic compounds Vinyl toluene, α- and p-Methylstyrol, alpha-Butylstyrol, 4- n-Butylstyrene, 4-n-Decylstyrene, and preferably styrene. Examples for nitriles Methacryl is nitrile. Vinyl halogenides Ethylenic unsaturated substituted with Chlorine, Fluorine or Bromine compounds, preferably Vinyl chloride and Vinylidene chloride. As vinyl ether, eg Vinyl Methylether or and vinyl isob'uthyl ether. Vinyl ether of alcohols containing 1 to 4 carbon atoms is preferred. is done. As hydrocarbons having 4 to 8 carbon atoms and two olefinic double bonds Butadiene, isoprene and Chloroprene are involved. Other monomers (d) 05- to C10-Alkyl acrylates and -methacrylates and Vinyl aromates, particularly Styrole and mixtures thereof are preferred. n-Hexil acrylate, Octyl acrylate and 2-Ethylhexyl acrylate, 2-Pr0pilheptyl acrylate, Styrole and these monomers mixtures are particularly preferred. Other monomers (d) containing eg hydroxyl groups Monomers are, in particular, C1-C10-Hydroxyalkyl (meth)acrylates and (meth)acrylamide. Other as monomers (d), also apart from Phenyloxy ethylglycol mono-(meth-)acrylate, Glycidyl acrylate, Glycidyl methacrylate, Amino-(meth-)acrylates and 2-Aminoethyl-(meth)acrylate.

Other monomers (d) are cross-linked monomers.

In one embodiment of the invention, the copolymer can be produced from: (a) one or more acyls selected from the group consisting of C1- to C4-Alkyl(meth)acrylates 79.5 to 99.5% by weight of monomer, (b) By weight of one or more acid monomers selected from Acryl acid and Methacrylic acid (c) 0-20% by weight Acrylnitrile and other monomers other than (a) to (0) There are no monomers.

The type and amount of monomers of the copolymer depend on the glass transition temperature of the emulsion polymer. As it will be between + 10 `C to + 45 ° C, preferably between + 15 ° C to + 40 ° C has been adapted. Glass transition temperature Differential Scanning Calorimetrie (ASTM D 3418- 08, "midpoint temperature").

The production of copolymers can occur via emulsion polymerization, then a emulsion polymer. In emulsion polymerization, normally ionic and/ or nonionic emulsifiers and/or protective colloids or stabilizers as active compounds to promote the dispersion of monomers in aqueous media used. Protective colloids are those that bind large amounts of water in solvating and polymer capable of stabilizing dispersions of insoluble polymers are compounds. Despite emulsifiers, they are normally formed between polymer particles and water. They do not reduce nerve surface tension. A detailed specification for suitable protective colloids Houben-Weyl, Metoden der organischen Chemie, Band XIV/1, Makromoleculare Stoffe, Georg- for example, amphiphilic polymers, that is, polymers with hydrophobic and hydrophilic groups. It is possible. It may be natural polymers such as starch or synthetic polymers. Emulsifiers There are both anionic and non-ionic nerve surfactants. their number average molecular weight is normally less than 2000 g/mol* or preferably below 1500 g/mol*, the numerical average of the protective colloids especially between 5000 and 50000 gmol. Preferably anionic and nonionic emulsifiers used as nerve surface active substrates. Suitable emulsifiers eg 3 to 50 ethoxylation ethoxylated C8- to C-fat alcohols having a degree of 3 to 50 ethoxylation ethoxylated M0n0-, Di- and Tri-C4- to C12-Alkyl-phenols having a grade of

Alkali metal salts of dialkyl esters of sulfobernseic acid, alkali metal salts of C8- to C12-Alkyl sulfates metal- and ammonium salts, C12- to Cia- alkali metal salts of acyl sulfonic acids and ammonium salts and ammonium salts of C9- to C1g-Alkylarylsulfonic acids. Emulsifiers and/or Protective colloids are used together as auxiliary agents to disperse monomers. otherwise, the amounts used are in the range of 0.1 to 5 °/o by weight, relative to the monomers.

Trade names of emulsifiers are, for example: D0wfax®2 A1, Emulan® NP 50, Dextrol® OC Lumiten® I-RA, Lumiten E 3065, Lumiten® ISC, Disponil ® NLS, Disponil LDBS 20, Disponil FES 77, Lutensol AT 18, Steinapol VSL, Emulphor NPS 25. Nerve surfactant substance normal They are used in amounts of 0.1 to 10% by weight, based on the polymerized monomers.

Emulsion polymerization normally at 30 °C to 1 30 °C, preferably 50 °C to 90 T: occurs between The polymerization center consists of both water alone, or water and It can also be used as mixtures of miscible liquids, such as methanol.

Preferably only water is used. Emulsion polymerization can be used both as a group process and also in the form of a feeding process, including step and gradient processing. applicable. polymerization, in which a part of the polymerization mixture is placed temperature, polymerize and then increase the polymerization mixture. normally contained in pure or emulsified form of one or more monomers. continuously or gradually over a number of volumetric separated feeds The feeding method is preferred.

Known and recognized excipients in emulsion polymerization, eg water-soluble initiators and regulators can be used. Water-soluble for emulsion polymerization initiators eg ammonium and alkali metal salts of peroxide sulfuric acid, eg Sodium peroxo disulphate, hydrogen peroxide or organic peroxides, for example tert-Butyl hydroperoxide.

Reduction oxidation (Red - Oks) initiator systems are also suitable. Red- Ox- initiator systems usually consist of inorganic at least one reducing agent and an inorganic or It also consists of organic oxidizing material. For example, in oxidation components There are initiators for the emulsion polymerization mentioned above.

In reducing components, for example, alkali metal salts of sulfuric acid, for example sodium sulfide, Sodium hydrogen sulfide, alkali salts of disulfuric acid, eg Sodium disulfide, Bisulfite addition compounds aliphatic aldehydes and ketos, eg acetone bisulfite or reducing agents for example hydroxy methane sulfinic acid or salts thereof or ascorbic acid.

Red-oxy-initiator systems dissolve soluble metal compounds, much of their metallic components by using soluble metal compounds that can occur in valence levels can be used. Known Red-Oxinitiator systems eg Ascorbic acid/ iron(II) sulphate! sodium peroxydisulfate, tert-Butyl hydroperoxide/ Sodium disulfide, tert-Butylhydroperoxide/ Na- Hydroxy methanesulfinic acid or tert-Butyl hydroperoxide/Ascorbic acid. individual components, eg reduction components can also be mixtures, eg hydroxymetal sulfonic acid it may be a mixture of sodium salt and sodium disulfide. The compounds mentioned are mostly It is used in the form of aqueous solutions, in which sub-concentration dispersion by the acceptable amount of water in it and by the upper concentration the water of the relevant compound Determined by its solubility in In general, the concentration is between 10 and 10. The amount of initiators is generally relative to the monomers polymerized. It is between 0.1 and 10% by weight, preferably between 0.5 and 5% by weight. lots of different Initiators can be used in emulsion polymerization. Removal of remaining monomers Initiator is normally added after the end of the noble emulsion polymerization. can be done.

In polymerization; 0 to 0.8 weight per 100 weight of monomers polymerized Regulators can be used in the amounts in the parts of the body, in this way the molar mass is reduced. For example Compounds having a thiol group are suitable, for example tert.-Butyl mercaptan, Mercapto ethyl propionate, 2-Ethylhexyl thioglycolate, Thio-glycol acidethyl ester, Mecapto ethanol, Merkapto Propii trimethoxysilane, n-Dodecyl mercaptan, or tert.-Dodecyl mercaptan. No thiol group regulators can be used, eg Terpinols. Emulsion as a preferred embodiment of at least one molecular polymer in the range of 0.05 to 0.5% by weight, based on the amount of monomer. Produced using a weight regulator.

The polymer dispersion used for the coating of packages is the only one for use according to the invention. It may consist of emulsion polymerization dispersed in water per head. But for example other such as fillers, antiblocking agents, dyes, flow agents or thickeners. may also contain additives.

In one embodiment of the invention, at least one copolymer contains 1 weight fraction relative to the copolymer. It is used in combination with platelet shaped pigments in the weight part. platelet Examples for shaped pigments are Talcum, clay or Micadir (mica). Talcum is preferred. Choice The shape factors (the ratio of length to thickness) are greater than 10.

The polymer dispersion forms a barrier layer after coating the substrate. A barrier layer especially for gaseous hexane of a coating with copolymer 23 *Cide with a permeability of less than d and an application weight of 20 - 25 g/m2 on paper available when a copolymer is used (described below) see measurement methods of samples).

The content of at least one copolymer in the dispersion used for the coating is preferably the most at least 1% by weight, in particular at least 5% by weight and up to °/o 60* by weight, or up to 75% by weight. Preferably at least one copolymer in an aqueous dispersion Its content is between 15 and 75% by weight, or between 40 and 60% by weight of Copolymers mPas, or a viscosity of 200 to 5000 mPas (Brookfield- On his viscometer, 20 UpM was measured at mile 4. Copolymer dispersed in aqueous dispersion are in between. This is for example optical microscopy, light scattering, or freeze diffraction electron can be detected by microscopy.

The carrier substrates according to the invention are at least those of the copolymers described above. coated with an aqueous dispersion of one. Suitable substrates are especially paper and cardboard.

The dispersions used for coating may contain other additives or auxiliary substances, for example rheology. thickeners, moistening aids or binders to adjust may contain.

Application Coating on paper or cardboard, for example on coating machines can be applied by applying the composition. Using sheet-shaped materials polymerization normally from a trough via an application roller as long as can be applied and leveled with the help of an airbrush. For the application of the coating possibilities, for example with the help of the Revers - Engraving method, spraying methods or a with a roller squeegee or other coating methods known to the person skilled in the art can occur with the help of The carrier substrate is here on at least one hundred coated, ie unilaterally or bilaterally coated. Paper and cardboard Preferred application methods for curtain coating, air squeegee, stick application or is not driving with a squeegee. Preferred application methods for foil coating are squeegee, squeegee, air squeegee. brush, reciprocating roller application methods, reciprocating engraving, pouring header or injector.

The amounts applied on flat materials are preferably 1 to 10 g per m2 (polymer, solid), preferably in foils of 2 to 7 g/m2, or preferably 5 to 30 g/m2 of paper or cardboard. Covering solvent or water after the compositions have been placed on the carrier substrate. evaporated. For this, for example, in continuous operation, the material is irradiated with an infrared irradiation device. It can be conveyed through a drying duct which may be equipped. After that it is covered and The dried material is conveyed over a cooling cylinder and finally wound. Dried thickness of the coating, preferably at least 1 µm, particularly 1 to 50 µm, particularly preferably 2 to 30 µm µm or 5 to 30 µm.

The barrier layer may be present on at least one of the packaging surfaces. A multi-layered may also form at least one of the many layers of the packaging coating. Barrier coating can be applied directly on a surface of the carrier material, the carrier and barrier other layers such as primary layers, other barrier layers or there may be layers of printing ink in color or black and white. The barrier layer is preferably It is located on the inner side of the package facing towards the packaging material.

The inner bag is preferably made of a polymer foil. The material of the inner bag is preferably polyolefin, preferably selected from polyethylene or oriented polypropylene, in which polyethylene both according to the high-pressure polymerization method and low-pressure polymerization It may be produced from ethylene according to the method. Further improvement of adhesion on a foil For this purpose, the carrier foil may first be subjected to a corona treatment. Other suitable carrier films foils of polyester, for example polyethylene terephthalate, polyamide, polystyrene and foils of polyvinyl chloride. Biologically in the carrier material in the form of an application. soluble foils, eg biodegradable aliphatic-aromatic copolyesters and/or polylactic acid, for example Ecoflex® - or Ecovio® foils. Suitable copolyecters for example from alkanediols, especially O2- to C8-Alkane diols, e.g. from 1,4-butanediol, aliphatic from dicarboxylic acids, especially C2- to C8-Dicarboxylic acids, for example Adipic acid and aromatic It is formed from dicarboxylic acids such as terephthalic acid.

The thickness of the carrier foils is generally between 10 and 200 pm.

In order to obtain special surface and coating properties of foils and packaging materials, for example, a good printability, improved barrier or block behavior, good water In addition, these desired properties of the coated substrates to obtain the strength by covering the barrier coating with cover layers that provide retention may be advantageous. Precoated substrates according to the invention have good appearance show their characteristics. Can be recoated according to one of the methods mentioned above or winding of paper or cardboard in between in a continuous process at the same time without opening. Many times, for example, using a curtain coater. can be coated. The barrier layer according to the invention is thus contained within the system, the surface its properties are then determined by the protective layer. protective layer barrier It has good adhesion to the layer.

The subject of the present invention is also a method for the production of a package, in which the above A composition in the form of the polymer dispersion described is put into use and a packaging It is placed on the substrate and dried, in which an aqueous polymer dispersion comprising at least one of the copolymers described above.

The subject of the present invention is also the formation of a barrier layer against volatile mineral oil components. an aqueous solution comprising at least one of the copolymers described above for the production of Polymer dispersion especially for the production of packaging, especially for foodstuffs It is used for the production of packaging.

The coated substrates according to the invention provide a very good barrier to volatile mineral oil components. show an effect. Coated substrates can thus be used as packaging material.

The coatings have very good mechanical properties and, for example, show good block behavior.

Examples If nothing other than composition is specified, percentage information always means percent by weight. carry. The information of an ingredient relates to the Content in aqueous solution or dispersion.

The following substances have been used: DlNP Diisononylphthalate MMA Methylmethacrylate MA Methylacrylate AS Acryl acid S Styrole nBA n-Butylacrylate AN Acrylnitrile This is Butadiene Test on the Oil Barrier A 10 x 10 cm sized sheet of blotting paper for examination of the oil barrier It is coated with a polymer and comes into contact with a test fat or test liquid (e.g. 2 ml fatty acid). is carried. The surface of the oiled area was measured at 60 cC after 16 hours. By quality x After hours, the indentation is evaluated.

Barrier test against gaseous mineral oil components (test method 1).

In an experiment structure, the following are packed on top of each other: 1. Donor ?iOg/m2 paper with 1 % 0/0 Gravex is contaminated 2. interval paper to eliminate a moistened contact, Câog/m2 3. Barrier material to be tested 4. Acceptor: commercially available PE-Foil 20 pm, LLDPE density 0.915 g/cm3 This package (basic size 10 x 10 cm) is wrapped in aluminum foil on all sides and sheathed.

The test system was stored at 60°C and one strip of the acceptor foil was periodically cut, 2 Mineral oil with n-hexane extraction at h/25°C and a carbon value of 15 - 25 analyzed by online HPLC-GC by measuring the content of its components. Metallic The entry time was determined for the oil components to indent through the barrier material. entry time, It is the time during which the mineral oil components in the extract are detected above the proof limit for the first time.

Barrier test against gaseous mineral oil components (test method 2) A sponge and 9 ml of hexane were placed in a cabinet and poured into an opening and a sealing ring. (inner diameter 63 mm). Openness will be strictly tested It is closed with barrier material and the barrier material is impregnated with hexane. It does not come into contact with the sponge. Cab weight reduction measured. weight reduction gas phase is a measure for the hexane escaping from the barrier material over It is a measure of the quality of the barrier effect against mineral oil components in the form of oil. Weight The decrease in grams is converted to 1 m2 paper surface and then expressed as g/m2 d (days). Comparison test oil barrier / barrier against gaseous mineral oil components Against fats and oils for polymers specified in Table 1, i.e. fatty acids and barrier effect (oil barrier) against fatty acid esters and gaseous mineral oil components, i.e. barrier against volatile hydrocarbons (below mineral oil barrier) were examined according to test 1. The results are summarized in the tables.

Table 1: Barrier effects of certain polymers Polymer Test coat Oil barrier Mineral oil barrier oil/ liquid aromatic/ aliphatic, amorphous Polyester- DINP + No penetration - Indent < 4d Polyurethane Aliphatic, partially crystalline Polyester- DINP + No penetration - Indent < 4d Polyurethane MMA/MA/AS Copolymer Tg approx. 50 °C DINP oil acid oiled aromatic/ aliphatic, partially crystalline DINP + No penetration - Indent < 4d Polyester- Polyurethane Polyethylene foil DINP oil + No penetration - Indent < 1d S/nBA/AN/AS Copolymer, Tg 5 °C fatty acid + No penetration - Indent < 4d S/Butadiene/AS Copolymer, Tg 20 °C fatty acid - completely - Hezan barrier no oiled (Test 2) The results show that gaseous mineral oil from coatings that have an oil barrier effect. It cannot be concluded that there is an activity as a barrier against its components. tested A mineral oil barrier when coated on MMA/MA/AS copolymer eg polyethylene although this polymer may stick to paper, possibly due to its high glass transition temperature. it does not form a good enough film and the coating has faulty places where the test oil can pass. has been found. Example 2: Production of polymer dispersions After washing with nitrogen in a reactor, 450.0 grams of demineralized water and 3.0 grams of Emulsifier (Disponil® LDBS 20 in 20% water) was placed. Mixture 70 cC - 90 cC is heated. Then 21.43 9 Sodium peroxo disulphate (7%) was added and it was taken for 50 minutes. in water) and 600.0 9 emulsion mixture consisting of monomer mixture according to the table was dosed into the reactor. 45 minutes after the end of emulsion feeding re-polymerized. The reactor was then cooled to room temperature. Solid content approximately: 45%.

Table 2: Copolymer compositions, amount information in % by weight example Monomer Tg [“C] dso [nm] 1) 1) weight-averaged particle size dso Example 3: Comparison test against gaseous mineral oil components Different barrier materials against gaseous mineral oil components by test method 2 The quality of the barrier effect has been tested. The results are shown in table 3.

Table 3: Barrier effects of certain polymers example Tg [“C] Hexane permeability [9 m2 d] B 1 10 0.2 - 0.3 B2 19 0.6 B 3 36 0.5 B 4 29 2 B 5 30 0.3 B 6 47 100-150 B7 47 120-160 B 8 33 1.8 B 9 36 2.1 The results show that the gaseous mineral oil of B1 to Bö, BB and 89 of the examples according to the invention. It shows that it has very good barrier properties against its components.

Claims (14)

REQUESTS 1. A package of paper or cardboard, in which the package is produced from recycled paper, at least partially contaminated with mineral oil, and the package contains at least a barrier layer, which is at least one copolymer that can be produced by emulsion polymerization of the following can be produced by applying an aqueous polymer dispersion containing (a) one or more acyl monomers selected from the group consisting of C1- to C4-Alkyl(meth)acrylates (b) from 0.1% by weight of one or more acid monomers 5*i, (c) 0 - 20% by weight Acryl nitrile and (d) °/o 0 to 10 by weight other monomers other than monomers (a) to (0), in which the glass transition temperature of the copolymer is + 10 °C to + It is located at 45 °C, in which the copolymer is made up of at least 70% by weight acyl monomers (a), in which the barrier layer may be present on at least one of the packaging surfaces or the barrier layer muscle can form at least one of the plurality of layers of a multilayer packaging coating. 2. A package according to the previous claim, where the amount of acid monomer (b) used is between 0.5 and 5% by weight, based on the sum of all monomers. Packaging according to one of the preceding claims, wherein the acyl monomers (a) are selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate and n-BL'iyl-acrylate. Packaging according to one of the preceding claims, wherein the copolymer consists of (a) 79.5% to 99.5% by weight of one or more acyl monomers selected from the group consisting of C1- to C4-alkyl(meth)acrylates, (b) acryl One or more acid monomers selected from acid and Methacrylic acid are produced from 0 - 20% by weight (c) Acrylnitrile and are obtained by the absence of other monomers different from (a) to (0) monomers. 5. A package according to one of the previous claims, wherein the glass transition temperature of the copolymer is between 15 °C and + 40 °C. 6. A package according to one of the previous claims, wherein the copolymer can be produced from 1 - 20% by weight acrylnitrile. 7. Packaging according to one of the previous claims, comprising of other monomers (d) C5- to C20-Alkyl(meth)acrylates, vinyl esters of carbon acids containing up to 20 carbon atoms, vinyl aromates having up to 20 carbon atoms, ethylenically unsaturated nitriles different from acryl nitrile. , vinyl halogenides, vinyl ethers of alcohols containing 1 to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 carbon atoms, and one or two double bonds and mixtures of these monomers. 8. The package according to one of the previous claims, in which 1 weight part of the copolymer in combination with platelet shaped pigments is up to 1 weight part of the copolymer. 9. A package according to one of the previous claims, wherein the copolymer and the coating have a permeability for gaseous n-hexane of less than 50 g/m2 d at 23 cC and an application weight of 20 to 25 g/m2 on paper. Package according to one of the preceding claims, wherein the copolymer is contained in the aqueous polymer dispersion in an amount of 15 to 75% by weight, preferably 40 to 60% by weight. 11.0 A package according to one of the preceding claims, wherein mineral oil contamination is caused by printing dyes and contains volatile paraffins, volatile naphthenes and/or volatile aromatic hydrocarbons. 12. A package according to one of the previous claims, wherein the barrier layer has a thickness between 2 and 30 pm. Method for the production of a package according to claim 1, wherein a composition in the form of an aqueous polymer dispersion is put into use, placed on a packaging substrate and dried, according to at least one of claims 1 to 10, wherein the aqueous polymer dispersion is relative to the polymer dispersion. comprising at least one copolymer having properties. 14. Use of an aqueous polymer dispersion comprising at least one copolymer having properties according to the polymer dispersion according to at least one of claims 1 to 10, for the production of a barrier layer against volatile mineral oil components.