DE102004001992A1 - Packaging material, useful for liquids and beverages, comprises an at least two layer laminate of paper or card sized with a polymer sizing agent and at least one water-impermeable film - Google Patents

Abstract

A packaging material comprises an at least two layer laminate comprising sized paper or card and at least one water-impermeable film for the production of packaging for liquids whereby the paper or card is sized with a polymer sizing agent.

Description

The The invention relates to a packaging material of at least one two-layer composite of glued paper or glued cardboard and at least one water-impermeable film for the packaging of liquids and the use of paper products that are sized in the mass and the one or both sides with a plastic film or metal are laminated, for the production of containers for packaging of liquids, especially of drinks.

Out EP-B-0 292 975 is the use of an alkyl ketene dimer emulsion in combination with a cationic resin glue and an insolubilizer Means like alum, for the production of cardboard for the packaging of liquids known. The production of the cardboard is done by adding sizing agent and alum to an aqueous slurry of Cellulose fibers and dewatering of the pulp on a sieve.

Out EP-A-1 091 043 is a process for producing a coated one Packaging cartons known, wherein an aqueous slurry of Cellulose fibers in the mass with an aqueous dispersion of a resin glue, a synthetic sizing agent such as alkyl ketene dimer and at least an aluminum compound and the aqueous slurry drained a sieve. The watery Optionally, dispersions of the sizing agents may be a dispersant contained, e.g. cationic starch, casein, Cellulose derivatives, polyvinyl alcohols, polyacrylamides or polyethyleneimines. The cardboard is usually following and the sizing coated.

both sides with a liquid-impermeable layer laminated paper products for the packaging of foodstuffs are known from WO-A-02/090206. The paper products are in bulk with aqueous dispersions of alkyl ketene dimers glued. The amount of alkyl ketene dimers is at least 0.25% by weight, preferably 0.25-0.4 Wt .-%, based on the weight of the dry paper products.

Further multilayer packaging materials, their base layer of paper or paperboard are described, for example, in WO-A-97/02140, WO-A-97/02181 and WO-A-98/18680 described.

Out The prior art is also known, sizing mixtures of aqueous dispersions of alkylketene dimers and polymer sizes for mass selection of paper and cardboard to use, cf. DE-A-32 35 529, WO-A-94/05855 and WO-A-96/31650.

Out the older one DE application 10237913.0 is a process for producing cardboard for the Packaging of liquids known. The cardboard is in this process by mass sizing an aqueous slurry of cellulose fibers with at least one sizing agent in Presence of at least one retention agent and at least one cationic polymers and optionally a water-soluble Aluminum compound and drainage of the pulp produced on a sieve. As a sizing agent are alkylketene dimers, alkyl and alkenyl succinic anhydrides, Alkyl isocyanates, combinations of rosin size and alum, and combinations from reaction products of rosin size with carboxylic acid anhydrides and alum.

Of the present invention is based on the object, other packaging materials on the basis of paper products, the Packaging in particular improved edge penetration and have improved adhesion of the laminates to paper or cardboard should.

The Task is solved according to the invention with a Packaging material of at least two-layer composite made of glued paper or glued cardboard and at least one impermeable Foil for the production of containers for the Packaging of liquids, if the paper or the cardboard in each case in bulk with a polymer sizing agent is glued.

The invention also provides the use of paper products, which are each available by
Machine sizing of a paper stock from an aqueous slurry of cellulosic fibers with at least one polymer sizing agent as a sizing agent or with a polymer sizing agent and an aq aqueous dispersion of an alkyl ketene dimer or mixtures thereof in the presence of a retention agent and optionally a water-soluble aluminum compound and optionally at least one cationic polymer,
Dewatering the stock on the wire of a paper machine,
Drying of the paper product and
one or both sides lamination of the paper product with a film of a plastic or metal,
for the production of containers for the packaging of liquids, in particular of beverages.

For the production From glued paper or glued cardboard you can all, usually Use cellulose fibers used in the paper industry, e.g. Fibers of wood pulp and all annual plants. Under wood pulp For example, one understands groundwood, thermomechanical material (TMP), chemothermomechanical material (CTMP), pressure ground, semichemical, High yield pulp, Refiner Mechanical Pulp (RMP) and waste paper. Furthermore Suitable pulps are bleached or unbleached Shape can be used. Examples of this are sulphate, sulphite and Natronzellstoffe. Preferably, unbleached pulps are used, which are also referred to as unbleached Kraft pulp. The Fibers can used alone or mixed with each other.

at The sizing of paper or cardboard is done during the sizing process Manufacturing process of these materials by going to the pulp Add a so-called engine sizing agent and place it on the sieve a paper machine drained under sheet formation. According to the invention as Masseleimungsmittel a polymer sizing agent of synthetic Used polymers. In the known from JP-A-58/115 196 polymer sizing agents it is watery Polymer dispersions that are a sizing agent for paper and at the same time increase the strength of paper. These dispersions are prepared by polymerizing, for example Styrene and alkyl acrylates in the presence of starch and free radicals Polymerization initiators in aqueous Medium made. The particular starch used is digested before the polymerization or even mined, so that they soluble in water is. The polymers of these dispersions are graft polymers of Styrene and alkyl acrylates on starch or modified starch.

Further polymer sizing agents are known from EP-B-0 257 412 and EP-B-0 267 770. They are prepared by copolymerizing acrylonitrile and / or methacrylonitrile and at least one acrylic acid ester of monohydric, saturated C ₃ - to C ₈ -alcohol in the manner of emulsion polymerization in an aqueous solution containing a degraded starch in the presence of free-radical initiators, preferably hydrogen peroxide or redox initiators. The degraded starches have viscosities η _i of 0.04 to 0.50 dl / g. Such starches are obtained, for example, by an oxidative, thermal, acidolytic or enzymatic degradation of a native, cationically or anionically modified starch. Advantageously, native starches from potatoes, wheat, corn. Rice or tapioca used. Preference is given to an enzymatically degraded potato starch. The degraded starches act as emulsifiers in the copolymerization of, for example, styrene and n-butyl acrylate in an aqueous medium. The aqueous solution in which the copolymerization is carried out, for example, contains 1 to 25 wt .-% of at least one degraded starch. In 100 parts by weight of such a solution is polymerized, for example, 10 to 150, preferably 40 to 100 parts by weight of the above monomers. Instead of acrylonitrile and / or methacrylonitrile and styrene can be used in the copolymerization, cf. WO-A-94 / 05,855th This gives aqueous dispersions of copolymers having an average particle diameter of, for example, 50 to 500 nm, preferably 100 to 300 nm. These polymer dispersions are presumably graft polymers of the monomers used in each case on degraded starch.

Further polymer sizing agents based on copolymers of styrene and C ₃ - to C ₈ -alkyl (meth) acrylates are known from WO 02/14393. They are prepared by copolymerizing said monomers in an aqueous medium in the presence of degraded starch and free radical polymerization initiators by a two-step process.

• (a) Styrol, Acrylnitril und/oder Methacrylnitril,
• (b) Acrylsäure- und/oder Methacrylsäureester von C₁- bis C₁₈-Alkoholen und/oder Vinylester von gesättigtem C₂- bis C₄-Carbonsäuren und ggf.
• (c) anderen monoethylenisch ungesättigten copolymerisierbaren Monomeren

in wäßriger Lösung in Gegenwart von 1 Gew.-Teil eines Lösungscopolymerisats aus

• (1) Di-C₁- bis C₄-Alkylamino-C₂- bis C₄-Alkyl(meth)acrylaten, die ggf. protoniert oder quaterniert sein können,
• (2) nichtionischen, hydrophoben, ethylenisch ungesättigten Monomeren, bei diesen Monomeren, wenn sie für sich alleine polymerisiert werden, hydrophobe Polymerisate bilden und ggf.
• (3) monoethylenisch ungesättigten C₃- bis C₅-Carbonsäuren oder ihren Anhydriden, wobei das Molverhältnis von (1) : (2) : (3) = 1 : 2,5 bis 10 : 0 bis 1,5 beträgt, copolymerisiert.

Suitable polymer sizes are also those aqueous polymer dispersions which can be prepared in the presence of synthetic polymeric protective colloids. They are obtainable, for example, by copolymerizing 2 to 32 parts of a mixture of

• (a) styrene, acrylonitrile and / or methacrylonitrile,
• (b) acrylic acid and / or methacrylic acid esters of C ₁ - to C ₁₈ -alcohols and / or vinyl esters of saturated C ₂ - to C ₄ -carboxylic acids and optionally
• (c) other monoethylenically unsaturated copolymerizable monomers

in aqueous solution in the presence of 1 part by weight of a Lösungscopolymerisats

• (1) di-C ₁ - to C ₄ -alkylamino-C ₂ - to C ₄ -alkyl (meth) acrylates which may optionally be protonated or quaternized,
• (2) nonionic, hydrophobic, ethylenically unsaturated monomers, in these monomers, when they are polymerized by themselves, form hydrophobic polymers and optionally
• (3) monoethylenically unsaturated C ₃ to C ₅ carboxylic acids or their anhydrides, wherein the molar ratio of (1): (2): (3) = 1: 2.5 to 10: 0 to 1.5 copolymerized.

A solution copolymer is first prepared in which the monomers of groups (1) and (2) and optionally (3) are copolymerized in a water-miscible organic solvent. Suitable solvents are, for example, C ₁ - to C ₃ -carboxylic acids, such as formic acid, acetic acid and propionic acid or C ₁ - to C ₄ -alcohols, such as methanol, ethanol, n-propanol or isopropanol and ketones, such as acetone. As the monomers of the group (1), dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate and dimethylaminopropyl acrylate are preferably used. The monomers of group (1) are preferably used in protonated or in quaternized form. Suitable quaternizing agents are, for example, methyl chloride, dimethyl sulfate or benzyl chloride.

Monomers of group (2) use nonionic, hydrophobic, ethylenically unsaturated compounds which, when polymerized by themselves, form hydrophobic polymers. These include, for example, styrene, methylstyrene, C ₁ - to C ₁₈ -alkyl esters of acrylic acid or methacrylic acid, for example methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate and isobutyl acrylate and isobutyl methacrylate, n-butyl methacrylate and tert-butyl methacrylate , Also suitable are acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate and vinyl butyrate. It is also possible to use mixtures of the monomers of group 2 in the copolymerization, for example mixtures of styrene and isobutyl acrylate. The solution copolymers serving as emulsifier may optionally also contain monomers of group (3) in copolymerized form, for example monoethylenically unsaturated C ₃ - to C ₅ -carboxylic acids or their anhydrides, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride or itaconic anhydride. The molar ratio of (1) :( 2) :( 3) is 1: 2.5 to 10: 0 to 1.5. The copolymer solutions thus obtained are diluted with water and serve in this form as a protective colloid for the polymerization of the abovementioned monomer mixtures of components (a) and (b) and, if appropriate, (c). Suitable monomers of group (a) are styrene, acrylonitrile, methacrylonitrile or mixtures of styrene and acrylonitrile or of styrene and methacrylonitrile. As monomers of group (b) are used acrylic acid and / or methacrylic acid esters of C ₁ - to C ₁₈ -alcohols and / or vinyl esters of saturated C ₂ - to C ₄ -carboxylic acids. This group of monomers corresponds to the monomers of group (2) already described above. Preferably used as monomer of group (b) butyl acrylate and butyl methacrylate, for example, acrylic acid isobutyl acrylate, acrylic acid n-butyl acrylate and methacrylic acid isobutyl acrylate. Monomers of group (c) are, for example, C ₃ to C ₅ monoethylenically unsaturated carboxylic acids, acrylamidomethylpropanesulfonic acid, sodium vinylsulfonate, vinylimidazole, N-vinylformamide, acrylamide, methacrylamide and N-vinylimidazoline. From 1 to 32 parts by weight of a monomer mixture of components (a) to (c) are used per 1 part by weight of the copolymer. The monomers of components (a) and (b) can be copolymerized in any ratio, for example in a molar ratio of 0.1: 1 to 1: 0.1.

The Monomers of group (c) are modified if necessary the properties of the copolymers used.

sizing agents of this type are described for example in EP-B-0 051 144, EP-B-0 058 313 and EP-B-0 150 003.

As a polymer sizing agent is preferably used aqueous polymer dispersions obtained by copolymerizing
From 20 to 65% by weight of styrene, acrylonitrile and / or methacrylonitrile,
80 to 35 wt .-% of acrylic acid and / or methacrylic acid esters of monohydric saturated C ₃ - to C ₈ -alcohols and
0 to 20 wt .-% of other monoethylenically unsaturated copolymerizable monomers such as acrylamide, methacrylamide, vinyl formamide, acrylic acid, methacrylic acid, maleic acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid or basic monomers such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl or dimethylaminopropyl, wherein the basic monomers usually used as hydrochlorides or in quaternized form with methyl chloride, dimethyl sulfate or benzyl chloride,
in the presence of radical-forming initiators in the manner of emulsion polymerization in an aqueous solution of a degraded starch are available as a protective colloid.

Furthermore, it is preferable to use, as polymer sizing agent, aqueous polymer dispersions which are obtained by copolymerizing
60 to 90% by weight of styrene and / or methylstyrene,
10 to 40 wt .-% 1,3-butadiene and / or isoprene and
0 to 20 wt .-% of other monoethylenically unsaturated copolymerizable monomers such as acrylic acid, methacrylic acid, itaconic acid, acrylamide, methacrylamide or N-vinylpyrrolidone,
in the presence of radical-forming initiators in the manner of emulsion polymerization in an aqueous solution of a degraded starch are available as a protective colloid. The polymer sizing agents are preferably cationic or anionic. The charge of the aqueous dispersions is based either on the type of comonomers copolymerized in the copolymers, for example when basic monomers are used, the polymer size dispersion is cationic, while it becomes anionic by copolymerizing, for example, acrylic acid or its salts, or else on the charge of the particular protective colloid used , For example, the use of cationic starch as an emulsifier leads to cationically adjusted polymer size dispersions.

For the engine simmering of paper or cardboard is set, for example, 0.1 to 2.0, preferably 0.2 to 0.75 weight percent polymer sizing agent (i.e., 100 percent polymer), based on dry paper product.

In addition, the sizing of paper and cardboard can be carried out in the presence of aqueous dispersions of reactive sizing agents such as alkylketene dimers, C ₅ -C ₂₂ -alkyl and / or C ₅ -C ₂₂ -alkenylsuccinic anhydrides, chloroformates and C ₁₂ -C ₃₆ -alkyl isocyanates, and in the presence of combinations of rosin size and alum or combinations of reaction products of rosin size with carboxylic acid anhydrides and alum. Instead of alum or in combination with alum, it is possible to use other aluminum-containing compounds such as polyaluminum chlorides or the polyaluminum compounds known from EP-B-1 091 043.

Of the reactive sizing agents, preference is given to using C ₁₂ - to C ₂₂ -alkyl ketene dimers, for example stearyldiketene, lauryldiketene, palmityldiketene, oleyldiketene, behenyldiketene or mixtures thereof.

suitable succinic are e.g. decenylsuccinic, octenyl succinic anhydride, dodecenylsuccinic and n-hexadecenyl succinic anhydride.

The Reactive sizing agents become common in the form of an aqueous Dispersion used. For example, alkyl ketene dimers are dispersed in an aqueous solution a cationic strength or one uses nonionic or anionic emulsifiers for Stabilization of alkylketene dimers. Depending on the type and quantity of used emulsifiers or mixtures of compatible with each other Emulsifiers are the resulting reactive size dispersions cationic, neutral or anionic charged.

For example, anionic emulsifiers can be added to alkyl ketene dimer dispersions which have been emulsified in water with the aid of cationic starch. If the charge of the anionic emulsifiers outweighs the charge of the cationic emulsifiers, an anionically charged Alkylketendimerdispersion. Anionically charged aqueous alkyldiketene dispersions are preferably prepared by emulsifying alkyl ketene dimers in aqueous solutions of anionic emulsifiers. As anionic emulsifiers, it is possible to use, for example, condensates of naphthalenesulfonic acid and formaldehyde, sulfonated polystyrene, C ₁₀ -C ₂₂ -alkylsulfuric acids, lignosulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid or the sodium, potassium or ammonium salts of said acids. Copolymers of acrylic acid and maleic acid, homopolymers of acrylic acid, homopolymers of methacrylic acid, copolymers of isobutene and maleic acid and / or acrylic acid, hydrolyzed copolymers of isobutene or diisobutene and maleic anhydride are suitable emulsifiers for the preparation of anionic Alkylketendimerdispersionen. The acid groups of the homopolymers and copolymers may for example be partially or completely neutralized with sodium hydroxide solution, potassium hydroxide solution or with ammonia and used in this form as anionic emulsifiers. The molecular weight M _{w of} the homo- and copolymers is, for example, from 1000 to 15 000 and is preferably in the range from 1500 to 10000. The emulsifiers are used, for example, in amounts of up to 3.5% by weight, preferably up to 2% by weight. , based on the reactive sizing agent to be dispersed.

The reactive sizing agents are optionally used in the engine sizing of the paper products to be used according to the invention as a carrier material for the packaging materials. They are used in particular when packaging materials with a particularly good edge penetration are desired. They are then used in amounts commonly used for making sized paper products are required, for example 0.1 to 2.0, preferably 0.1 to 0.5 wt .-%, based on dry cellulose fibers. For example, from 0 to 90 parts by weight, preferably from 50 to 90 parts by weight, of reactive sizing agents are used per 100 parts by weight of polymer sizing agent. When using mixtures of a polymer size agent dispersion and an aqueous dispersion of a reactive sizing agent, the mixtures contain, in each case based on the polymer content, for example, 5 to 50, preferably 10 to 30 wt .-% polymer (100%).

Provided Reactive sizing agents used together with a polymer sizing agent can be, the reactive sizing agent, preferably alkyl ketene dimer dispersions, first to Add paper stock and then meter the polymer size dispersions. However, it is also possible to use the alkyl ketene dimer dispersion and at least a polymer sizing agent dispersion simultaneously to the stock inflict and then drain it under foliation or you can put a mixture of a reactive size such as at least one alkyl ketene dimer dispersion and at least one Polymer size dispersion to the pulp and dehydrates it then under sheet formation.

The Polymer size can Of course also as a surface sizing agent can be used by adding them e.g. with the help of a size press on the surface of the paper or sprayed onto the surface of the paper.

The Drain the pulp is additionally in the presence of a retention aid. In addition to anionic retention aids or nonionic retention aids such as polyacrylamides prefers cationic polymers as retention aids and as drainage aids used. This will significantly improve runnability reached the paper machines. As a cationic retention agent can one all for that Commercially available Use products. These are, for example, cationic polyacrylamides, Polydiallyldimethylammonium chlorides, polyethyleneimines, polyamines with a molecular weight of more than 50 000, polyamines, if necessary modified by grafting of ethyleneimine, polyetheramides, Polyvinylimidazoles, polyvinylpyrrolidines, polyvinylimidazolines, Polyvinyl tetrahydropyrines, poly (dialkylaminoalkyl vinyl ethers), poly (dialkylaminoalkyl (meth) acrylates) in protonated or quaternized form as well as polyamidoamines from a dicarboxylic acid like adipic acid and polyalkylenepolyamines such as diethylenetriamine amine which are reacted with ethyleneimine grafted and with polyethylene glycol dichlorohydrin ethers according to the teaching DE-B-24 34 816 are cross-linked or polyamidoamines with epichlorohydrin too water-soluble Condensation products are reacted and copolymers of Acrylamide or methacrylamide and dialkylaminoethyl acrylates or methacrylates, for example copolymers of acrylamide and Dimethylaminoethyl acrylate in the form of the salt with hydrochloric acid or in quaternized with methyl chloride form. Other suitable retention agents are so-called microparticle systems made of cationic polymers like cationic starch and finely divided silica or from cationic polymers such as cationic polyacrylamide and Bentonite.

The cationic polymers used as retention aids, For example, Fikentscher has K values of at least 140 (determined in 5% aqueous saline at a polymer concentration of 0.5 wt .-%, a temperature of 25 ° C and a pH of 7). They are preferably in amounts of 0.01 to 0.3 wt .-%, based on dry cellulose fibers used.

To the aqueous slurry of Cellulosic fibers may optionally be added to those already mentioned Substances added to at least one cationic polymer. Examples for cationic Polymers are polymers containing vinylamine units, vinylguanidine units containing polymers, dialkylaminoalkyl (meth) acrylamide units containing polymers, polyethyleneimines grafted with ethyleneimine Polyamidoamines and / or polydiallyldimethylammonium chlorides. The Men ge of cationic polymers, for example, from 0.001 to 2.0 wt .-%, preferably 0.01 to 0.1 wt .-%, based on dry Cellulose fibers.

Vinylamine units containing polymers are known, cf. US-A-4,421,602, US-A-5,334,287, EP-A-0 216,387, US-A-5,981,689, WO-A-00/63295 and US-A-6,121,409. you will be by hydrolysis of open-chain N-vinylcarboxamide units Made of polymers. These polymers are e.g. available through Polymerizing N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide and N-vinylpropionamide. The monomers mentioned can either polymerized alone or together with other monomers.

Suitable monoethylenically unsaturated monomers which are copolymerized with the N-vinylcarboxamides are all compounds which can be copolymerized therewith. Examples of these are vinyl esters of saturated carboxylic acids of 1 to 6 carbon atoms such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate and vinyl ethers such as C ₁ - to C ₆ -alkyl vinyl ethers, for example methyl or ethyl vinyl ether. Other suitable Comonomers are esters, amides and nitriles of ethylenically unsaturated C ₃ - to C ₆ -carboxylic acids, for example methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate, acrylamide and methacrylamide and also acrylonitrile and methacrylonitrile.

Further suitable carboxylic acid esters are derived from glycols or polyalkylene glycols, respectively only one OH group is esterified, e.g. Hydroxyethyl acrylate, hydroxyethyl methacrylate, Hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, Hydroxybutylmethacrylat and acrylic acid monoesters of polyalkylene glycols a molecular weight of 500 to 10,000. Other suitable comonomers are Esters of ethylenically unsaturated carboxylic acids with amino alcohols such as, for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, Diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, Dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate and diethylaminobutyl acrylate. The basic acrylates can be used in Form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or Nitric acid, salts with organic acids like formic acid, Acetic acid, propionic or the sulfonic acids or used in quaternized form. Suitable quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, Ethyl chloride or benzyl chloride.

Further suitable comonomers are amides ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids with alkyl radicals of 1 to 6 carbon atoms, e.g. N-methylacrylamide, N, N-dimethylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-propylacrylamide and tert. Butylacrylamide and basic (meth) acrylamides, such. dimethylaminoethyl, Dimethylaminoethylmethacrylamide, diethylaminoethylacrylamide, diethylaminoethylmethacrylamide, Dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and diethylaminopropylmethacrylamide.

Farther are suitable comonomers N-vinylpyrrolidone, N-vinylcaprolactam, Acrylonitrile, methacrylonitrile, N-vinylimidazole and substituted N-vinylimidazoles, e.g. N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole and N-vinylimidazolines such as N-vinylimidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-ethylimidazoline. N-vinylimidazoles and N-vinylimidazolines except in the form of the free bases also in neutralized with mineral acids or organic acids or used in quaternized form, the quaternization preferably with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride is made. Also suitable are diallyldialkylammonium halides such as. Diallyl dimethyl ammonium chloride.

• – 95 bis 5 mol-%, vorzugsweise 90 bis 10 mol-% mindestens eines N-Vinylcarbonsäureamids und
• – 5 bis 95 mol-%, vorzugsweise 10 bis 90 mol-% andere, damit copolymerisierbare monoethylenisch ungesättigte Monomere

in einpolymerisierter Form. Die Comonomeren sind vorzugsweise frei von Säuregruppen.The copolymers contain, for example

• From 95 to 5 mol%, preferably from 90 to 10 mol%, of at least one N-vinylcarboxamide and
• From 5 to 95 mol%, preferably from 10 to 90 mol%, of other monoethylenically unsaturated monomers copolymerizable therewith

in copolymerized form. The comonomers are preferably free of acid groups.

• – N-Vinylformamid mit
• – Vinylformiat, Vinylacetat, Vinylpropionat, Acrylnitril, N-Vinylcaprolactam, N-Vinylharnstoff, N-Vinylpyrrolidon oder C₁- bis C₆-Alkylvinylethern

und anschließende Hydrolyse der Homo- oder der Copolymerisate unter Bildung von Vinylamineinheiten aus den einpolymerisierten N-Vinylformamideinheiten erhältlich sind, wobei der Hydrolysegrad z.B. 5 bis 100 mol-%, vorzugsweise 70 bis 100 mol-% beträgt. Die Hydrolyse der oben beschriebenen Polymerisate erfolgt nach bekannten Verfahren durch Einwirkung von Säuren, Basen oder Enzymen. Bei Verwendung von Säuren als Hydrolysemittel liegen die Vinylamineinheiten der Polymerisate als Ammoniumsalz vor, während bei der Hydrolyse mit Basen die freie Aminogruppen entstehen.In order to prepare polymers containing vinylamine units, preference is given to homopolymers of N-vinylformamide or of copolymers obtained by copolymerizing

• - N-vinylformamide with
• - Vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile, N-vinylcaprolactam, N-vinyl urea, N-vinylpyrrolidone or C ₁ - to C ₆ alkyl vinyl ethers

and subsequent hydrolysis of the homopolymers or the copolymers to form vinylamine units from the polymerized N-vinylformamide units are obtainable, wherein the degree of hydrolysis, for example, 5 to 100 mol%, preferably 70 to 100 mol%. The hydrolysis of the above-described polymers is carried out by known methods by the action of acids, bases or enzymes. When acids are used as hydrolyzing agents, the vinylamine units of the polymers are present as the ammonium salt, while hydrolysis with bases gives rise to the free amino groups.

In most cases, the degree of hydrolysis of the homopolymers and copolymers is 80 to 95 mol%. The degree of hydrolysis of the homopolymers is synonymous with the content of the polymers of vinylamine units. For copolymers containing vinyl esters in copolymerized form, in addition to the hydrolysis of the N-vinylformamide units, hydrolysis of the ester groups to form vinyl alcohol units may occur. This is especially the case when carrying out the hydrolysis of the copolymers in the presence of sodium hydroxide solution. Polymerized acrylonitrile is also chemically altered upon hydrolysis. This entste For example, amide groups or carboxyl groups. The vinylamine units containing homo- and copolymers may optionally contain up to 20 mol% of amidine units, for example, by reaction of formic acid with two adjacent amino groups or by intramolecular reaction of an amino group with an adjacent amide group, for example, of copolymerized N-vinylformamide. The molecular weights M _{w of} the polymers containing vinylamine units are, for example, 500 to 10 million, preferably 1000 to 5 million (determined by light scattering). This molar mass range corresponds, for example, to K values of 5 to 300, preferably 10 to 250 (determined according to H. Fikentscher in 5% strength aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 0.5% by weight).

The Vinylamine polymers containing polymers are preferably in used salt-free form. Salt-free aqueous solutions of vinylamine units containing polymers for example, from the salt-containing polymer solutions described above Help of ultrafiltration on suitable membranes at separation limits from, for example, 1000 to 500,000 daltons, preferably 10,000 up to 300 000 daltons are produced. Also the ones described below aqueous solutions of amino and / or Ammonium group-containing other polymers can by means of ultrafiltration be obtained in salt-free form.

Derivatives of polymers containing vinylamine units can also be used as cationic polymers. It is thus possible, for example, to prepare a large number of suitable derivatives from the vinylamine units by amidation, alkylation, sulfonamide formation, urea formation, thiourea formation, carbamate formation, acylation, carboxymethylation, phosphonomethylation or Michael addition of the amino groups of the polymer. Of particular interest in this case are uncrosslinked polyvinylguanidines which are obtained by reaction of polymers comprising vinylamine units, preferably polyvinylamines, with cyanamide (R ¹ R ² N-CN, where R ¹ , R ² = H, C ₁ - to C ₄ -alkyl, C ₃ - C ₆ -Cycloalkyl, phenyl, benzyl, alkyl-substituted phenyl or naphthyl mean), cf. US-A-6,087,448, column 3, line 64 to column 5, line 14.

To The polymers containing vinylamine units also belong hydrolyzed graft polymers of, for example, N-vinylformamide on polyalkylene glycols, polyvinyl acetate, polyvinyl alcohol, polyvinylformamides, Polysaccharides such as starch, Oligosaccharides or monosaccharides. The graft polymers are available through that he for example, N-vinylformamide in an aqueous medium in the presence at least one of the said grafting together, if appropriate radically polymerized with copolymerizable other monomers and the grafted vinylformamide units subsequently in hydrolyzed to Vinylamineinheiten known manner.

When cationic polymers also include polymers of dialkylaminoalkyl (meth) acrylamides into consideration. Suitable monomers for the preparation of such polymers are, for example, dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, Dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, Diethylaminoethylacrylamide, diethylaminoethylmethacrylamide and diethylaminopropylacrylamide. These Monomers can in the form of free bases, salts with inorganic or organic Acids or be used in quaternized form in the polymerization. You can to homopolymers or together with other copolymerizable Monomers to copolymers are radically polymerized. The For example, polymers contain at least 30 mole percent, preferably at least 70 mol .-.% Of the said basic monomers copolymerized.

Further suitable cationic polymers are polyethyleneimines, for example by polymerization of ethyleneimine in aqueous solution in the presence of acid-releasing Compounds, acids or Lewis acids can be produced as a catalyst. For example, polyethyleneimines have Molar masses up to 2 million, preferably from 200 to 1,000,000. Particularly preferred are polyethyleneimines having molar masses of 500 to 750,000 used. The polyethyleneimines may optionally be modified be, e.g. alkoxylated, alkylated or amidated. You can also get one Michael addition or a plug synthesis are subjected. The available Derivatives of polyethylenimines are also cationic polymers suitable.

Also contemplated are ethyleneimine-grafted polyamidoamines which are obtainable, for example, by condensing dicarboxylic acids with polyamines and then grafting ethyleneimine. Suitable polyamidoamines are obtained, for example, by reacting dicarboxylic acids having 4 to 10 carbon atoms with polyalkylenepolyamines which contain 3 to 10 basic nitrogen atoms in the molecule. Examples of dicarboxylic acids are succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. In the preparation of polyamidoamines can also be mixtures of Use dicarboxylic acids, as well as mixtures of several polyalkylene polyamines. Suitable polyalkylenepolyamines are, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine. The dicarboxylic acids and polyalkylenepolyamines are heated to higher temperatures, for example to temperatures in the range from 120 to 220, preferably 130 to 180 ° C., in order to prepare the polyamidoamines. The water produced during the condensation is removed from the system. If appropriate, it is also possible to use lactones or lactams of carboxylic acids having 4 to 8 C atoms in the condensation. For example, from 0.8 to 1.4 moles of a polyalkylenepolyamine are used per mole of a dicarboxylic acid. These polyamidoamines are grafted with ethyleneimine. The grafting reaction is carried out, for example, in the presence of acids or Lewis acids, such as sulfuric acid or boron trifluoride etherates, at temperatures of, for example, 80 to 100.degree. Compounds of this type are described for example in DE-B-24 34 816.

The optionally crosslinked polyamidoamines, which are optionally additionally grafted before crosslinking with ethyleneimine, are suitable as cationic polymers. The crosslinked, with ethyleneimine grafted polyamidoamines are water-soluble and have, for example, a mean molecular weight M _w of 3000 to 2 million daltons. Typical crosslinkers are, for example, epichlorohydrin or bischlorohydrin ethers of alkylene glycols and polyalkylene glycols.

When cationic polymers are also polyallylamines into consideration. polymers of this kind are obtained by homopolymerization of allylamine, preferably in with acids neutralized form or by copolymerizing allylamine with other monoethylenically unsaturated Monomers described above as comonomers for N-vinylcarboxamides.

Also suitable are water-soluble crosslinked polyethyleneimines which are obtainable by reaction of polyethyleneimines with crosslinkers such as epichlorohydrin or bischlorohydrin ethers of polyalkylene glycols having 2 to 100 ethylene oxide and / or propylene oxide units and still have free primary and / or secondary amino groups. Also amide polyethylenimines are suitable, for example, by amidation of polyethyleneimines with C ₁ - to C ₂₂ monocarboxylic acids are available. Further suitable cationic polymers are alkylated polyethyleneimines and alkoxylated polyethyleneimines. For example, in the alkoxylation, from 1 to 5 ethylene oxide or propylene oxide units are used per NH unit in the polyethyleneimine.

The The above-mentioned cationic polymers have e.g. K values of 8 to 300, preferably 15 to 180 (determined by H. Fikentscher in 5% aqueous Saline at 25% and a polymer concentration of 0.5% by weight). At a pH value of 4.5, they have for example a charge density of at least 1, preferably at least 4 meq / g polyelectrolyte.

Preferred cationic polymers are polymers containing vinylamine units and polyethyleneimines. Examples for this are:
Vinylamine homopolymers, 10 to 100% hydrolyzed polyvinylformamides, partially or completely hydrolyzed copolymers of vinylformamide and vinyl acetate, vinyl alcohol, vinylpyrrolidone or acrylamide, each having molecular weights of 3,000 to 2,000,000 and
Polyethyleneimines, cross-linked polyethyleneimines or amidated polyethyleneimines, each having molecular weights of 500 to 3,000,000.

Of the Polymer content of the aqueous solution is, for example 1 to 60, preferably 2 to 15 and usually 5 to 10 wt .-%.

The Production of cardboard is usually done by draining a slurry of cellulose fibers. Preference is given to the use of kraft pulp. Of particular interest is the use of TMP and CTMP. The pH of the cellulose fiber slurry is for example 4 to 8, preferably 6 to 8. The drainage of the pulp may be discontinuous or continuous be made of a paper machine. The order of addition of cationic polymer, engine sizing agent and retention aid can be chosen arbitrarily become. But preferred is a procedure in which one to the aqueous cellulose fiber slurry first the Retention agent and then the cationic polymer, preferably Polyvinylamine, and subsequently at least one reactive sizing agent such as alkyl ketene dimer, alkyl or alkenyl succinic anhydride in combination with an aluminum compound or a mixture adds this engine sizing agent and a polymer sizing agent. According to one another embodiment will be first at least one polymer sizing agent, then the retention agent and finally dosed the cationic polymer.

at the production of the paper products to be used according to the invention you can others, usually co-use eligible tools, e.g. Fixer, Dyes, bactericides and dry and / or wet strength agents for paper.

After dewatering the paper stock and drying the paper product, a mass-sized cardboard having a weight per unit area of 80 to 400 g / m ² , preferably 120 to 220 g / m ^{2, is obtained} . The cardboard is coated on one or both sides with a film of plastic or metal such as aluminum.

suitable Plastic films can made of polyethylene, polypropylene, polyamide or polyester. The slides can for example with the aid of an adhesive with the sized paper products get connected. In such cases One mostly uses films which are coated with an adhesive are and squeeze the composite. But you can also see the surface of the Coated sized paper products with an adhesive and the Then apply one or both sides of the film and the resulting film Press compound. The slides can but also directly by the action of heat and pressure with the Cardboard be processed into a composite, from which then the appropriate Structure for the production of the packaging for liquids be cut out. The packages are preferably on used in the food sector, e.g. for packing drinks like Mineral water, juices or milk or for the production of drinking vessels such as cups. In these Packaging depends on having good edge penetration feature, i.e. the cardboard should be as possible little or practically no liquid take up. The adhesion of films to those with polymer sizes sized paper products are better than those of films Paper products exclusively are sized with alkylketene dimers.

If if nothing else results from the context, the percentages mean in the examples weight percent. The K values were calculated according to H. Fikentscher, Cellulose Chemistry, Vol. 13, 58-64 and 71-74 (1932) in 5% aqueous saline a temperature of 25 ° C and a pH of 7 at a polymer concentration of 0.5% by weight. certainly. The molecular weights Mw of the polymers were determined by light scattering measured.

determination the edge penetration

The cardboard produced in each case is laminated on both sides with a polyethylene tape. You then determine the thickness of the box. From the cardboard test strips of size 25 × 75 mm are then cut and weighed in each case. In order to determine the edge penetration, the test strips are immersed in a bath containing a 30% strength hydrogen peroxide solution heated to 70 ° C. The test strips are removed from the bath after a residence time of 10 minutes. Excess hydrogen peroxide is taken up with filter paper. The test strips are weighed again. From the increase in weight, one then calculates the edge penetration in kg / m ² .

Ink flotation time

The Ink swimming time (measured in minutes) is the time that a test ink according to DIN 53126 until 50% penetration through a test sheet needed.

Cobb value

Determination was carried out according to DIN 53 132 by storage of the paper sheets for a period of 60 seconds in water. The water absorption is given in g / m ² .

Examples 1 to 6

To a paper stock having a fabric density of 10 g / l of 100% unbleached pine sulfate pulp with a freeness of 20 ° SR (Schopper-Riegler) was added, based on dry stock, 0.75% of a cationic starch (solvitose BPN) as a retention aid and adjusted the pH of the mixture to 7. Then metered in each case the amounts given in the table stearyidiketene in the form of an aqueous dispersion (Basoplast ^® 4118MC) and an aqueous dispersion of said polymer size also in Table 1. The fiber slurries were each mixed and dewatered on a Rapid-Kothen sheet former. Sheets were obtained with a basis weight of 150 g / m ² .

The following polymer size agents were used:
A polymer size: Basoplast 250D ^® (aqueous dispersion of a copolymer prepared by emulsion polymerization of acrylonitrile and n-butyl acrylate in the presence of degraded cationic starch as an emulsifying agent and hydrogen peroxide as initiator).

Polymer size B: Basoplast 265D ^® (aqueous dispersion of a copolymer prepared by emulsion polymerization of styrene and n-butyl acrylate in the presence of degraded cationic starch as an emulsifying agent and hydrogen peroxide as initiator).

Polymer size C: Basoplast PR8172 ^® (aqueous dispersion of a copolymer prepared by emulsion polymerization of styrene and n-butyl acrylate in the presence of cationic starch as an emulsifying agent and hydrogen peroxide as initiator).

Table 1

The leaves were then dried on a steam-heated drying cylinder at a temperature of 90 ° C to a water content of 6-10%. After drying, the Cobb value of the leaves was determined. The sheets were then laminated on both sides with a sheet of polyethylene of density 0.918 g / cm ³ (heating the composite under pressure to ° C). Thereafter, one determined the edge penetration of the three-layer composite. The results are shown in Table 3.

Comparative Examples 1 to 4

To a paper stock having a fabric density of 10 g / l of 100% unbleached pine sulfate pulp with a freeness of 20 ° SR (Schopper-Riegler) was added, based on dry stock, 0.75% of a cationic starch (solvitose BPN) as a retention aid and adjusted the pH of the mixture to 7. Then metered in each case the amounts given in Table 2 to stearyidiketene in the form of an aqueous dispersion (Basoplast ^® 4118MC). Thereafter, the aqueous fiber slurries were each mixed together and dewatered on a Rapid-Kothen sheet former to give a paper product having a basis weight of 150 g / m ² .

Table 2

The leaves were subsequently on a steam-heated drying cylinder at a temperature of 90 ° C on a water content of 6-10% dried. After drying, the Cobb value of the leaves was determined. The leaves were subsequently glued on both sides with a polyethylene film (pressing the Composite under pressure). Then you determined the edge penetration of the three-layered composite with respect to hydrogen peroxide. The Results are given in Table 3.

Table 3

Claims (12)

Packaging material of at least two layers of glued paper or glued cardboard and at least one water-impermeable film for the manufacture of containers for the packaging of liquids, characterized in that the paper or board is in each case glued with a polymer sizing agent. Packaging material according to claim 1, characterized that the paper or the cardboard in each case in bulk with a polymer sizing agent is glued. Packaging material according to claim 1, characterized that the paper or cardboard is in each case in the surface with a polymer sizing agent is sized. Packaging material according to claim 1, characterized that the paper or cardboard additionally in the presence of aqueous Dispersions of reactive sizes and / or combinations of resin size and alum is glued on. Packaging material according to claim 1 or 2, characterized characterized in that the paper or cardboard is available by successively adding aqueous alkyl ketene dispersions and aqueous Polymer size dispersions to the pulp and dewatering of the pulp on the screen of a paper machine. Packaging material according to one of claims 1 or 2, characterized in that the paper or cardboard is available by simultaneous addition of aqueous Alkylketene dimer dispersions and aqueous polymer size dispersions to the pulp and dewatering of the pulp on the screen of a paper machine. Packaging material according to claim 1 or 2, characterized characterized in that the paper or cardboard is available by sizing with a sizing mixture of an aqueous Polymer size dispersion and an aqueous alkyl ketene dimer dispersion. Packaging material according to one of claims 1 to 7, characterized in that the paper or cardboard additionally in Presence of cationic polymers is sized. Packaging material according to one of claims 1 to 8, characterized in that the paper or the cardboard respectively on both sides with a water-impermeable plastic film and / or metal is laminated. Packaging material according to one of claims 1 to 9, characterized in that the paper or cardboard on one or both sides with a film of polyethylene, polypropylene, copolymer of ethylene and Propylene, polyester, polyvinyl alcohol, copolymer of ethylene and vinyl acetate, copolymer of ethylene and vinyl alcohol, polyamide and / or aluminum laminated. Packaging material according to one of claims 1 to 8, characterized in that the paper or cardboard has a basis weight of 80 to 400 g / m ² and is laminated on both sides with a film of polyethylene. Use of paper products, each available by (i) mass sizing of a paper stock from an aqueous one slurry of cellulose fibers with at least one polymer sizing agent or with a polymer sizing agent and an aqueous dispersion of an alkyl ketene dimer or mixtures thereof in the presence of a retention agent and optionally a water-soluble Aluminum compound and optionally at least one cationic polymers (ii) dewatering of the pulp on the screen of a paper machine, (iii) drying of the paper product and (iv) one or two sided lamination the paper product with a film of a plastic or metal, to Production of containers for the Packaging of liquids, especially of drinks.