EP1210480B1 - Method of producing paper, paperboard and cardboard - Google Patents

Abstract

Paper, board and cardboard are produced by a process in which a paper stock is drained in the presence of condensates of basic amino acids with sheet formation. In particular, homo- and cocondensates of lysine and the crosslinked condensates obtainable therefrom by reaction with crosslinking agents are used in amounts of from 0.01 to 5% by weight, based on dry paper stock, as a means of increasing the dry and wet strength and the absorptivity of paper, for fixing anionic dyes and interfering substances in the paper, for increasing the drainage rate and the retention as well as the efficiency of synthetic anionic and cationic retention aids in the production of paper, board and cardboard by draining a paper stock with sheet formation.

Description

The invention relates to a method for producing paper, Cardboard and cardboard by draining paper stock in the presence of polymers.

It is common knowledge that paper consists essentially of fibers consisting of wood and / or cellulose and optionally of mineral fillers, in particular calcium carbonate and / or aluminum silicate, and that the essential process in papermaking consists of a separation of this fiber - And fillers consists of a dilute aqueous suspension of these substances by means of one or more movable screens. It is also known that certain chemicals are added to the suspension of fiber and fillers in water both to improve this separation process and to achieve or improve certain properties of the paper. A very current overview of commonly used paper chemicals and their application can be found, for example, in - Paper Chemistry, JC Roberts ed., Blackie Academic & Professional, London, Second edition 1996, - and in - Applications of Wet-End Paper Chemistry, CO Au and I. Thorn eds., Blackie Academic & Professional, London, 1995.

Many of the paper chemicals used are, as can be seen from the cited literature, cationic water-soluble polymers or, in other words, cationic polyelectrolytes or polycations with preferably medium or high molecular mass. These products are added to the very thin paper pulp before the paper sheet is formed on the sieve. Depending on their composition, they cause, for example, more fine material to remain on the sieve, or that the water on the sieve is separated more quickly, or that certain substances are fixed to the paper fibers and thus do not get into the white water, with the latter property both The cleanliness of the white water can be in the foreground, as well as the effect of the fixed substances, such as dyes or sizing agents, on the properties of the finished paper. However, polycations can also increase the strength of the paper or give the paper improved residual strength when wet. In order to obtain this so-called wet strength, however, polycations are generally used which additionally carry reactive groups, which react with the paper constituents or with themselves with the formation of a network and which make the paper more resistant to water due to the covalent bonds formed.

From US-A-5 556 938 it is known that the thermal polycondensation of Amino acids in the presence of organic or inorganic acids. As Animoacids are, for example, aspartic acid, alanine, arginine, glycine, lysine and Called tryptophan. The condensates available in this way are used, for example, in washing machines and Cleaning agents, as scale inhibitors, as dispersants for pigments and as Dispersant used in papermaking.

From US-A-3 869 342 are cationic, thermosetting resins based on Polyamidoamines known to crosslink by reaction with epichlorohydrin and by Heating can be hardened. Resins of this type are used, for example, as wet strength agents used in the manufacture of paper.

In the state of the art used for the purposes mentioned Polycations are almost exclusively Polymers of synthetic origin, i.e. to products on petrochemical Base. A major exception are, however cationic strengths arising from the reaction of a raw material vegetable based with a synthetic cationizing agent emerge. In rare cases, others with synthetic Cationizing agents modified polysaccharides in the Papermaking, such as cationic guar flour. In In literature, the polysaccharide chitosan, which one obtained by chemical reaction on chitin from shellfish, as cationic paper aid described, but so far is none permanent practical application has become known.

Regardless of their special impact profiles, products have often based on plant or animal raw materials Advantage that when reintroduced into the natural cycle are more easily biodegradable. The use of raw materials Plant-based also helps protect fossil fuels Resources and to reduce carbon emissions at.

In the case of the polycations previously used as paper chemicals based on renewable raw materials polysaccharides with a very narrow activity profile. The main one cationic strengths are used to increase the dry strength of the paper used and to a lesser extent Dimensions also as a retention aid.

The object of the invention is based on further substances to provide natural raw materials that are used in the Paper production, for example, anionic substances in paper fix and improve the retention of fillers.

(i) Homokondensaten basischer Aminosäuren, Kondensaten aus mindestens zwei basischen Aminosäuren und/oder Cokondensaten aus basischen Aminosäuren und cokondensierbaren Verbindungen mit

(ii) mindestens einein Vernetzer mit mindestens zwei funktionellen Gruppen erhältlich sind.

Kondensate leiten sich beispielsweise von Homo- oder Cokondensaten von Lysin, Arginin, Ornithin und/oder Tryptophan ab. Sie sind z.B. dadurch erhältlich, daß man

(a) Lysin, Arginin, Ornithin, Tryptophan oder deren Gemische mit

(b) mindestens einer damit cokondensierbaren Verbindung

kondensiert. Die Polymeren werden durch Kondensation von

(a) Lysin, Arginin, Ornithin, Tryptophan oder deren Gemische mit

(b) mindestens einer Verbindung aus der Gruppe der Monoamine, Diamine, Triamine, Tetraamine, Monoaminocarbonsäuren, Lactame, aliphatischen Aminoalkohole, Harnstoff Guanidin, Melamin, Carbonsäuren, Carbonsäureanhydride, Diketene, nicht-proteinogene Aminosäuren, Alkohole, alkoxylierten Alkohole, alkoxylierten Amine, Aminozucker, Zucker und deren Gemische

hergestellt. Von besonderem technischen Interesse sind hierbei Cokondensate, die durch Kondensation von

(a) Lysin und

(b) mindestens einer Verbindung aus der Gruppe der C₆- bis C₁₈-Alkylamine, Lactame mit 5 bis 13 C-Atomen im Ring, nichtproteinogenen Aminosäuren, Monocarbonsäuren, polybasische Carbonsäuren, Carbonsäureanhydriden und Diketenen

erhältlich sind.The object is achieved according to the invention with a process for the production of paper, cardboard and cardboard by dewatering a paper stock in the presence of polymers with sheet formation if crosslinked condensates are used as polymers which are produced by reaction of

(i) homocondensates of basic amino acids, condensates of at least two basic amino acids and / or cocondensates of basic amino acids and cocondensable compounds with

(ii) at least one is available in a crosslinker with at least two functional groups.

Condensates are derived, for example, from homo- or cocondensates of lysine, arginine, ornithine and / or tryptophan. They are available, for example, in that one

(a) Lysine, arginine, ornithine, tryptophan or their mixtures with

(b) at least one compound co-condensable therewith

condensed. The polymers are made by condensation of

(a) Lysine, arginine, ornithine, tryptophan or their mixtures with

(b) at least one compound from the group of the monoamines, diamines, triamines, tetraamines, monoaminocarboxylic acids, lactams, aliphatic amino alcohols, urea guanidine, melamine, carboxylic acids, carboxylic acid anhydrides, diketenes, non-proteinogenic amino acids, alcohols, alkoxylated alcohols, alkoxylated amines, alkoxylated amines , Sugar and their mixtures

manufactured. Of particular technical interest here are cocondensates, which are obtained by condensation of

(a) lysine and

(b) at least one compound from the group of the C ₆ - to C ₁₈ -alkylamines, lactams with 5 to 13 C atoms in the ring, non-proteinogenic amino acids, monocarboxylic acids, polybasic carboxylic acids, carboxylic acid anhydrides and diketenes

are available.

The connections of groups (a) and (b) are, for example, in molar ratio of 100: 1 to 1:20, preferably 100: 1 to 1: 5 and usually in a molar ratio of 10: 1 to 1: 2 in the condensation used.

(i) Homokondensaten basischer Aminosäuren und/oder Kondensaten aus mindestens zwei basischen Aminosäuren und/ oder
Cokondensaten aus basischen Aminosäuren und cokondensierbaren Verbindungen mit

(ii) mindestens einem Vernetzer mit mindestens zwei funktionellen Gruppen.>

Crosslinked condensates of basic amino acids are suitable as polymers for paper production. Such crosslinked condensates can be obtained, for example, by reacting

(i) homocondensates of basic amino acids and / or condensates of at least two basic amino acids and / or
Cocondensates from basic amino acids and cocondensable compounds with

(ii) at least one crosslinker with at least two functional groups.>

The basic amino acids lysine, arginine, ornithine and tryptophan which can be considered as a compound of group (a) in the condensation can be in the form of the free bases, the hydrates, the esters with C ₁ - to C ₄ -alcohols and the salts such as sulfates, Hydrochlorides or acetates can be used in the condensation. Lysine hydrate and aqueous solutions of lysine are preferably used. Lysine can also be used in the form of the cyclic lactam, α-amino-ε-caprolactam. Lysine mono- or dihydrochloride or mono- or dihydrochloride of lysine esters can also be used. If the salts of compounds of group (a) are used, equivalent amounts of inorganic bases, for example sodium hydroxide solution, potassium hydroxide or magnesium oxide, are preferably used in the condensation. The alkobol component of mono- and dihydrochlorides of lysine esters are derived, for example, from low-boiling alcohols, for example methanol, ethanol, isopropanol or tert-butanol. L-lysine dihydrochloride, DL-lysine monohydrochloride and L-lysine monohydrochloride are preferably used in the condensation.

Examples of co-condensable compounds of group b) are aliphatic or cycloaliphatic amines, preferably methylamine, Ethylamine, propylamine, butylamine, pentylamine, hexylamine, Heptylamine, octylamine, nonylamine, decylamine, undecylamine, Dodecylamine, tridecylamine, stearylamine, palmitylamine, 2-ethylhexylamine, Isononylamine, hexamethylene diamine, dimethylamine, Diethylamine, dipropylamine, dibutylamine, dihexylamine, ditridecylamine, N-methylbutylamine, N-ethylbutylamine, cyclopentylamine, cyclohexylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine and Dicyclohexylamine.

Of the diamines, triamines and tetraamines are preferably suitable Ethylene diamine, propylene diamine, butylene diamine, neopentyl diamine, Hexamethylene diamine, octamethylene diamine, imidazole, 5-amino-1,3-trimethylcyclohexylmethylamine, diethylene triamine, Dipropylenetriamine and tripropyltetraamine. Other suitable amines are 4,4'-methylenebiscyclohexylamine, 4,4'-methylenebis (2-methylcyclohexylamine), 4,7-dioxadecyl-1,10-diamine, 4,9-dioxadodecyl-1,12-diamine, 4,7,10-trioxatridecyl-1,13-diamine, 2- (ethylamino) ethylamine, 3- (methylamino) propylamine, 3- (cyclohexylamino) propylamine, 3- (2-aminoethyl) aminopropylamine, 2- (diethylamino) ethylamine, 3- (dimethylamino) propylamine, dimethyldipropylenetriamine, 4-aminomethyloctane-1,8-diamine, 3- (diethylamino) propylamine, N, N-diethyl-1,4-pentanediamine, diethylenetriamine, dipropylenetriamine, Bis (hexamethylene) triamine, aminoethylpiparazine, aminopropylpiperazine, N, N-bis (aminopropyl) methylamine, N, N-bis (aminopropyl) ethylamine, N, N-bis (aminopropyl) methylamine, N, N-bis (aminopropyl) ethylamine, N, N-bis (aminopropyl) hexylamine, N, N-bis (aminopropyl) octylamine, N, N-dimethyldipropylenetriamine, N, N-bis (3-dimethylaminopropyl) amine, N, N'-1,2-ethanediylbis (1,3-propanediamine), N- (hydroxyethyl) piperazine, N- (aminoethyl) piperazine, N- (aminopropyl) piperazine, N- (aminoethyl) morpholine, N- (aminopropyl) morpholine, N- (aminoethyl) imidazole, N- (aminopropyl) imidazole, N- (aminoethyl) hexamethylene diamine, N- (aminopropyl) hexamethylene diamine, N- (aminoethyl) ethylenediamine, N- (aminopropyl) ethylenediamine, N- (aminoethyl) butylene diamine, N- (aminopropyl) butylene diamine, Bis (aminoethyl) piparazin, bis (aminopropyl) piparazin, Bis (aminoethyl) hexamethylenediamine, bis (aminopropyl) hexamethylenediamine, Bis (aminoethyl) ethylene diamine, Bis (aminopropyl) ethylenediamine, bis (aminoethyl) butylenediamine, Bis (aminopropyl) butylenediamine, oxypropylamines such as preferred Hexyloxyamine, octyloxyamine, decyloxyamine and dodecyloxyamine.

Aliphatic amino alcohols are, for example, 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 2- (2-aminoethoxy) ethanol, 2 - [(2-aminoethyl) amino] ethanol, 2-methylaminoethanol, 2- (ethylamino) ethanol, 2-butylaminoethanol, diethanolamine, 3 - [(hydroxyethyl) amino] -1-propanol, Diisopropanolamine, bis (hydroxyethyl) aminoethylamine, Bis (hydroxypropyl) minoethylamin, Bis (hydroxyethyl) aminopropylamine and bis (hydroxypropyl) aminopropylamine.

a) Lysin mit

b) Hexamethylendiamin, Octylamin, Monoethanolamin, Octamethylendiamin, Diaminododecan, Decylamin, Dodecylamin, Caprolactam, Laurolactam, Aminocapronsäure, Aminolaurinsäure oder deren Mischungen erhältlich sind.

Suitable monoaminocarboxylic acids are preferably glycine, alanine, sarcosine, asparagine, glutamine, 6-aminocaproic acid, 4-aminobutyric acid, 11-aminolauric acid, lactams with 5 to 13 carbon atoms in the ring such as caprolactam, laurolactam or butyrolactam. Glucosamine, melamine, urea, guanidine, polyguanidine, piperidine, morpholine, 2,6-dimethylmorpholine and tryptamine are also suitable. Polymers are particularly preferred which are obtained by condensation of

a) Lysine with

b) hexamethylene diamine, octylamine, monoethanolamine, octamethylene diamine, diaminododecane, decylamine, dodecylamine, caprolactam, laurolactam, aminocaproic acid, aminolauric acid or mixtures thereof are available.

Further co-condensable compounds b) are, for example, saturated Monocarboxylic acids, unsaturated monocarboxylic acids, polybasic Carboxylic acids, carboxylic anhydrides, diketenes, monohydroxycarboxylic acids, monobasic polyhydroxycarboxylic acids and Mixtures of the compounds mentioned. Examples of saturated monobasic carboxylic acids are formic acid, acetic acid, propionic acid, Butyric acid, valeric acid, caproic acid, octanoic acid, Nonanoic acid, lauric acid, palmitic acid, stearic acid, arachidic acid, Behenic acid, myristic acid, 2-ethylhexanoic acid and all naturally occurring fatty acids and mixtures thereof.

Examples of unsaturated monobasic carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, sorbic acid, oleic acid, linoleic acid and erucic acid. Examples of polybasic carboxylic acids are oxalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, itaconic acid, adipic acid, aconitic acid, azelaic acid, pyridinedicarboxylic acid, furandicarboxylic acid, phthalic acid, terephthalic acid, diglycolic acid, glutaric acid, C substituted _{4-dicarboxylic} acids, sulfosuccinic acid, C ₁ - to C ₆ - Alkyl succinic acids, C ₂ -C ₂₆ alkenyl succinic acids, 1,2,3-propane tricarboxylic acid, 1,1,3,3-propane tetracarboxylic acid, 1,1,2,2-ethane tetracarboxylic acid, 1,2,3,4-butane tetracarboxylic acid, 1, 2,2,3-propanetetracarboxylic acid, 1,3,3,5-pentanetetracarboxylic acid, 1,2,4-benzenetricarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid. Examples of suitable carboxylic anhydrides are mono- and dianhydrides of butanetetracarboxylic acid, phthalic anhydride, acetylcitric anhydride, maleic anhydride, succinic anhydride, itaconic anhydride and aconitic anhydride.

a) Lysin mit

b) Laurinsäure, Palmitinsäure, Stearinsäure, Bernsteinsäure, Adipinsäure, Ethylhexansäure oder deren Mischungen erhältlich sind.

Polymers which are obtained by condensation of

a) Lysine with

b) Lauric acid, palmitic acid, stearic acid, succinic acid, adipic acid, ethylhexanoic acid or mixtures thereof are available.

As component b) are also alkyldiketenes with 1 to 30 carbon atoms in the alkyl group and diketene itself. Examples of alkyldiketenes are methyldiketene, hexyldiketene, Cyclohexyldiketene, octyldiketene, decyldiketene, dodecyldiketene, Palmityldiketene, stearyldiketene, oleyldiketene, octadecyldiketene, Eicosyldiketen, Docosyldiketen and Behenyldiketen.

Examples of monohydroxycarboxylic acids are malic acid, citric acid and isocitric acid. Are polyhydroxycarboxylic acids for example tartaric acid, gluconic acid, bis (hydroxymethyl) propionic acid and hydroxylated unsaturated fatty acids such as Dihydroxystearic.

As component b) further include non-proteinogenic amino acids into consideration, such as anthranilic acid, N-Methylaminosubstituierte acids such as N-methylglycine, dimethylaminoacetic acid, ethanolaminoacetic, N-Carboxymethylaminocarbonsäure, nitrilotriacetic acid, ethylenediamine acetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylenediaminotriacetic, diaminosuccinic acid, C ₄ - to C ₂₆ aminoalkyl carboxylic acid such as 4-aminobutyric acid, 6-aminocaproic acid and 11-aminoundecanoic acid. The acids can be used in the form of the free acids and also in the form of their salts with alkali metal bases or amines in the condensation.

Also suitable as component b) are alcohols, for example monohydric alcohols having 1 to 22 carbon atoms in the molecule, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, hexanol, 2 -Ethylhexanol, cyclohexanol, octanol, decanol, dodecanol, palmityl alcohol and stearyl alcohol. Other suitable alcohols are, for example, ethylene glycol, propylene glycol, glycerol, polyglycerols with 2 to 8 glycerol units, erythritol, pentaerythritol and sorbitol. The alcohols can optionally be alkoxylated. Examples of such compounds are the addition products of 1 to 200 moles of a C ₂ -C ₄ -alkylene oxide to one mole of an alcohol. Suitable alkylene oxides are, for example, ethylene oxide, propylene oxide and butylene oxides. Ethylene oxide or propylene oxide is preferably used, or both ethylene oxide and propylene oxide are added to the alcohols in the form of blocks, it being possible first to add a sequence of ethylene oxide units and then propylene oxide units to the alcohols, or first to add propylene oxide and then ethylene oxide to the alcohols. A statistical addition of ethylene oxide and propylene oxide and a different arrangement of the blocks in the alkoxylated products is also conceivable. Of particular interest are, for example, the addition products of 3 to 20 moles of ethylene oxide to one mole of a C ₁₃ / C ₁₅ oxo alcohol or to fatty alcohols. The alcohols can optionally contain a double bond, such as oleyl alcohol. As component (b) it is also possible to use alkoxylated amines which are derived, for example, from the amines given above and which can be obtained by reaction with ethylene oxide and / or propylene oxide. For example, the addition products of 5 to 30 mol ethylene oxide with 1 mol stearylamine, oleylamine or palmitylamine may be mentioned. Also possible as component (c) are naturally occurring amino sugars such as chitosan or chitosamine and compounds which can be obtained from carbohydrates by reductive amination, for example aminosorbitol. The condensation products can optionally contain, in condensed form, carbohydrates such as glucose, sucrose, dextrin, starch and degraded starch, maltose and sugar carboxylic acids such as gluconic acid, glutaric acid, glucuronactone and glucuronic acid.

The above components can be in the form of free Bases (such as amines) or in the form of the corresponding salts, e.g. the ammonium salts with inorganic or organic acids be used in the condensation. In the case of carboxylic acids you can the co-condensable compounds (b) in the form of free carboxylic acids or in the form of their alkali metal, alkaline earth metal or use ammonium salts in the condensation.

The condensation can be carried out in bulk, in an organic solvent or in an aqueous medium. The reaction can advantageously be carried out in an aqueous medium at concentrations of the compounds of groups (a) and (b), for example 10 to 98% by weight, at temperatures of 120 to 300 ° C. In a particularly preferred embodiment of the process for the preparation of such compounds, the condensation is carried out in water at concentrations of component (a) and (b) from 20 to 70% by weight under pressure at temperatures from 140 to 250 ° C. However, the condensation can also be carried out in an organic solvent such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide, glycol, polyethylene glycol, propylene glycol, polypropylene glycol, monohydric alcohols, addition products of ethylene oxide and / or propylene oxide with monohydric alcohols, with amines or with carboxylic acids. If starting from aqueous solutions of the reactants (a) and (b), the water can optionally also be distilled off before or during the condensation. The condensation can be carried out under normal pressure with removal of water. The water formed during the condensation is preferably removed from the reaction mixture. The condensation can be carried out under increased pressure, under normal pressure or under reduced pressure. The condensation time is, for example, between 1 minute and 50 hours, preferably 30 minutes to 16 hours. The condensation products have, for example, molecular weights M _w of 300 to 1,000,000, preferably 500 to 100,000.

The condensation can optionally also in the presence of Mineral acids can be carried out as a catalyst. The concentration of mineral acids is, for example, 0.001 to 5, preferably 0.01 to 1 wt .-%, based on the basic amino acids. Examples of suitable mineral acids as a catalyst are hypophosphorous acid, hypodiphosphoric acid, phosphorous Acid, hydrochloric acid, sulfuric acid or mixtures of the mentioned acids. Also the alkali, ammonium and alkaline earth metal salts of the acids can be used as a catalyst.

The following compounds are preferably used as crosslinking agents (ii) Consideration: α, ω- or vicinal dichloroalkanes, epihalohydrins, Bischlorohydrin ethers of polyols, bischlorohydrin ethers of polyalkylene glycols, Esters of chloroformic acid, phosgene, diepoxides, Polyepoxides, diisocyanates and polyisocyanates.

(1) Ethylencarbonat, Propylencarbonat und/oder Harnstoff,

(2) monoethylenisch ungesättigten Carbonsäuren und deren Estern, Amiden und Anhydriden, mindestens zweibasischen gesättigten Carbonsäuren oder Polycarbonsäuren sowie den jeweils davon abgeleiteten Estern, Amiden und Anhydriden,

(3) Umsetzungsprodukten von Polyetherdiaminen, Alkylendiaminen, Polyalkylenpolyaminen, Alkylenglykolen, Polyalkylenglykolen oder deren Gemischen mit monoethylenisch ungesättigten Carbonsäuren, Estern, Amiden oder Anhydriden monoethylenisch ungesättigter Carbonsäuren, wobei die Umsetzungsprodukte mindestens zwei ethylenisch ungesättigte Doppelbindungen, Carbonsäureamid-, Carboxyl- oder Estergruppen als funktionelle Gruppen aufweisen,

(4) mindestens zwei Aziridinogruppen enthaltenden Umsetzungsprodukten von Dicarbonsäureestern mit Ethylenimin

(5) Diepoxide, Polyepoxide, Diisocyanate und Polyisocyanate

sowie Mischungen der genannten Vernetzer.Halogen-free crosslinkers are used with particular advantage. The halogen-free crosslinkers are at least bifunctional and are preferably selected from the group consisting of:

(1) ethylene carbonate, propylene carbonate and / or urea,

(2) monoethylenically unsaturated carboxylic acids and their esters, amides and anhydrides, at least dibasic saturated carboxylic acids or polycarboxylic acids and the esters, amides and anhydrides derived therefrom in each case,

(3) reaction products of polyether diamines, alkylenediamines, polyalkylene polyamines, alkylene glycols, polyalkylene glycols or their mixtures with monoethylenically unsaturated carboxylic acids, esters, amides or anhydrides of monoethylenically unsaturated carboxylic acids, the reaction products being at least two ethylenically unsaturated double amide bonds or groups, carboxyl groups, carboxyl exhibit,

(4) at least two aziridino group-containing reaction products of dicarboxylic acid esters with ethyleneimine

(5) Diepoxides, polyepoxides, diisocyanates and polyisocyanates

and mixtures of the crosslinkers mentioned.

Suitable crosslinkers of group (1) are ethylene carbonate, Propylene carbonate and urea. From this group of monomers propylene carbonate is preferably used. The crosslinker of this group react to form urea compounds containing amino groups.

Suitable halogen-free crosslinkers of group (2) are, for example, monoethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid and the amides, esters and anhydrides derived therefrom. The esters can be derived from alcohols having 1 to 22, preferably 1 to 18, carbon atoms. The amides are preferably unsubstituted, but can carry a C ₁ -C ₂₂ -alkyl radical as a substituent.

   in der

R =

C₁- bis C₂₂-Alkyl,

R¹

= H, C₁- bis C₂₂-Alkyl und

n =

0 bis 22

charakterisiert werden. Außer den Dicarbonsäuren der Formel I eignen sich beispielsweise monoethylenisch ungesättigte Dicarbonsäuren wie Maleinsäure oder Itaconsäure. Die Ester der in Betracht kommenden Dicarbonsäuren leiten sich vorzugsweise von Alkoholen mit 1 bis 4 Kohlenstoffatomen ab. Geeignete Dicarbonsäureester sind beispielsweise Oxalsäuredimethylester, Oxalsäurediethylester, Oxalsäurediisopropylester, Bernsteinsäuredimethylester, Bernsteinsäurediethylester, Bernsteinsäurediisopropylester, Bernsteinsäuredi-n-propylester, Bernsteinsäurediisobutylester, Adipinsäuredimethylester, Adipinsäurediethylester und Adipinsäurediisopropylester. Geeignete Ester von ethylenisch ungesättigten Dicarbonsäuren sind beispielsweise Maleinsäuredimethylester, Maleinsäurediethylester, Maleinsäurediisopropylester, Itaconsäuredimethylester und Itaconsäurediisopropylester. Außerdem kommen substituierte Dicarbonsäuren und ihre Ester wie Weinsäure (D-, L-Form und als Racemat) sowie Weinsäureester, wie Weinsäuredimethylester und Weinsäurediethylester in Betracht.Further halogen-free crosslinkers of group (2) are at least dibasic saturated carboxylic acids such as dicarboxylic acids and the salts, diesters and diamides derived therefrom. These compounds can, for example, using the formula

in the

R =

C ₁ to C ₂₂ alkyl,

R ¹

= H, C ₁ to C ₂₂ alkyl and

n =

0 to 22

be characterized. In addition to the dicarboxylic acids of the formula I, monoethylenically unsaturated dicarboxylic acids such as maleic acid or itaconic acid are suitable, for example. The esters of the dicarboxylic acids in question are preferably derived from alcohols having 1 to 4 carbon atoms. Suitable dicarboxylic acid esters are, for example, dimethyl oxalate, diethyl oxalate, diisopropyl oxalate, dimethyl succinate, diethyl succinate, diisopropyl succinate, di-n-propyl succinate, diisobutyl amide and adipate adipate, adipate adipate. Suitable esters of ethylenically unsaturated dicarboxylic acids are, for example, dimethyl maleate, diethyl maleate, diisopropyl maleate, dimethyl itaconate and diisopropyl itaconate. Substituted dicarboxylic acids and their esters such as tartaric acid (D-, L-form and as a racemate) and tartaric acid esters such as tartaric acid dimethyl ester and tartaric acid diethyl ester are also suitable.

Suitable dicarboxylic anhydrides are, for example, maleic anhydride, Itaconic anhydride and succinic anhydride. The Crosslinking of compounds of the component containing amino groups (a) with the halogen-free crosslinking agents mentioned above takes place with the formation of amide groups or amides such as adipic acid diamide by Umamidierung. Maleic acid ester, monoethylenic Unsaturated dicarboxylic acids and their anhydrides can both by formation of carboxamide groups as well as by addition of NH groups of the component to be crosslinked (e.g. polyamidoamines) networking like a Michael addition cause.

At least dibasic saturated carboxylic acids include for example tri- and tetracarboxylic acids such as citric acid, Propane tricarboxylic acid, ethylenediaminetetraacetic acid and butanetetracarboxylic acid. Also come as crosslinkers of group (2) the salts derived from the aforementioned carboxylic acids, Esters, amides and anhydrides are considered.

Suitable crosslinkers of group (2) are also polycarboxylic acids, by polymerizing monoethylenically unsaturated Carboxylic acids or anhydrides are available. As monoethylenic unsaturated carboxylic acids come e.g. Acrylic acid, Methacrylic acid, fumaric acid, maleic acid and / or itaconic acid in Consideration. Suitable crosslinkers are e.g. polyacrylic acids, Copolymers of acrylic acid and methacrylic acid or copolymers from acrylic acid and maleic acid.

Further suitable crosslinkers (2) are prepared, for example, by polymerizing anhydrides such as maleic anhydride in an inert solvent such as toluene, xylene, ethylbenzene, isopropylbenzene or solvent mixtures in the presence of initiators which form free radicals. Peroxyesters such as tert-butyl per-2-ethylhexanoate are preferably used as initiators. In addition to the homopolymers, copolymers of maleic anhydride are suitable, for example copolymers of acrylic acid and maleic anhydride or copolymers of maleic anhydride and a C ₂ to C ₃₀ olefin.

For example, copolymers of maleic anhydride and isobutene or copolymers of maleic anhydride and diisobutene are preferred. The copolymers containing anhydride groups can optionally be modified by reaction with C ₁ -C ₂₀ alcohols or ammonia or amines and can be used in this form as crosslinking agents.

The molecular weight M _{w of} the homopolymers and copolymers is, for example, up to 10,000, preferably 500 to 5,000. Polymers of the type mentioned above are described, for example, in EP-A-0 276 464, US Pat. No. 3,810,834, GB-A-1 411 063 and US-A-4 818 795. The at least dibasic saturated carboxylic acids and the polycarboxylic acids can also be used as crosslinking agents in the form of the alkali metal or ammonium salts. The sodium salts are preferably used. The polycarboxylic acids can be partially, for example 10 to 50 mol%, or completely neutralized.

Compounds of group (2) which are preferably used are tartaric acid dimethyl esters, Tartaric acid diethyl ester, adipic acid dimethyl ester, Diethyl adipate, dimethyl maleate, diethyl maleate, Maleic anhydride, maleic acid, acrylic acid, Acrylic acid methyl ester, acrylic acid ethyl ester, acrylamide and methacrylamide.

• monoethylenisch ungesättigten Carbonsäuren,
• Estern monoethylenisch ungesättigter Carbonsäuren,
• Amiden monoethylenisch ungesättigter Carbonsäuren oder
• Anhydriden monoethylenisch ungesättigter Carbonsäuren.

Halogen-free crosslinkers of group (3) are, for example, reaction products of polyether diamines, alkylene diamines, polyalkylene polyamines, alkylene glycols, polyalkylene glycols or mixtures thereof

• monoethylenically unsaturated carboxylic acids,
• Esters of monoethylenically unsaturated carboxylic acids,
• Amides of monoethylenically unsaturated carboxylic acids or
• Anhydrides of monoethylenically unsaturated carboxylic acids.

The polyether diamines are, for example, by reacting Polyalkylene glycols made with ammonia. The polyalkylene glycols can be 2 to 50, preferably 2 to 40 alkylene oxide units contain. This can be, for example, polyethylene glycols, Polypropylene glycols, polybutylene glycols or block copolymers from ethylene glycol and propylene glycol, block copolymers from ethylene glycol and butylene glycol or block copolymers from ethylene glycol, propylene glycol and butylene glycol act. In addition to the block copolymers, are also suitable for Preparation of the polyether diamines, random copolymers from ethylene oxide and propylene oxide and optionally Butylene oxide. Polyether diamines are also derived from polytetrahydrofurans which have 2 to 75 tetrahydrofuran units. The polytetrahydrofurans are also reacted with Converted ammonia into the corresponding α, ω-polyether diamines. Preferably used for the preparation of the polyether diamines Polyethylene glycols or block copolymers of ethylene glycol and Propylene glycol.

in der X, Y, Z = O, NH
   und Y zusätzlich noch CH₂
   m, n = 0 - 4
   p, q = 0 - 45000
bedeuten.Examples of suitable alkylenediamines are ethylenediamine, propylenediamine, 1,4-diaminobutane and 1,6-diaminohexane. Suitable polyalkylene polyamines are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, bisaminopropylethylenediamine and polyethyleneimines having molecular weights up to 5000. The amines described above monoethylenically unsaturated carboxylic acids are reacted so with monoethylenically unsaturated carboxylic acids, esters, amides or anhydrides, that the resulting products have at least 2 ethylenically unsaturated double bonds, carboxamide, carboxyl or ester groups as functional groups. For example, when the amines or glycols in question are reacted with maleic anhydride, compounds are obtained which can be characterized, for example, using the formula II:

in the X, Y, Z = O, NH
and Y additionally CH ₂
m, n = 0-4
p, q = 0-45000
mean.

The compounds of formula (II) are, for example, thereby available that alkylene glycols, polyethylene glycols, polyethyleneimines, Polypropyleneimines, polytetrahydrofurans, α, ω-diols or α, ω-diamines with maleic anhydride or those given above other monoethylenically unsaturated carboxylic acids or Implemented carboxylic acid derivatives. The for the production of the Crosslinker II have suitable polyethylene glycols preferably molecular weights from 62 to 10,000, the molecular weights of the polyethyleneimines are preferably 129 to 50,000 that of the polypropylene imines 171 to 50,000. Suitable alkylene glycols are, for example Ethylene glycol, 1,2-propylene glycol, 1,4-butanediol and 1,6-hexanediol.

Preferably used α, ω-diamines are ethylenediamine and α, ω-diamines derived from approx. 400 to 5,000 each of molecular weights M _w of molecular weights M _w of polyethylene glycols or of polytetrahydrofurans.

Particularly preferred crosslinkers of the formula II are reaction products of maleic anhydride with α, ω-polyether diamines a molecular weight of 400 to 5000, the reaction products of polyethyleneimines with a molecular weight of 129 to 50,000 Maleic anhydride and the reaction products of ethylenediamine or triethylenetetramine with maleic anhydride in a molar ratio of 1: at least 2. When converting polyalkylene glycols or diols with monoethylenically unsaturated Carboxylic acids, their esters, amides or anhydrides are formed to obtain the double bond of the monoethylenically unsaturated Carboxylic acids or their derivatives crosslinkers, in which the monoethylenic unsaturated carboxylic acids or their derivatives an amide group with the polyether diamines, alkylene diamines or Polyalkylene polyamines and via an ester group with the alkylene glycols or polyalkylene glycols are linked. These implementation products contain at least two ethylenically unsaturated Double bonds. This type of crosslinker reacts with the amino groups the connections to be cross-linked in the manner of a Michael addition to the terminal double bonds of these crosslinkers and, if appropriate additionally with the formation of amide groups.

in der X, Y, Z = O, NH
   und Y zusätzlich noch CH₂
   R¹ = H, CH₃
   R² = H, COOMe, COOR, CONH₂
   R³ = OR, NH₂, OH, OMe
   R = C₁- bis C₂₂-Alkyl
   Me = H, Na, K, Mg, Ca
   m, n = 0 - 4
   p, q = 0 - 45000
bedeuten.Polyether diamines, alkylenediamines and polyalkylene polyamines can also react with maleic anhydride or the ethylenically unsaturated carboxylic acids or their derivatives with addition to the double bond in the manner of a Michael addition. This gives crosslinkers of the formula III

in the X, Y, Z = O, NH
and Y additionally CH ₂
R ¹ = H, CH ₃
R ² = H, COOMe, COOR, CONH ₂
R ³ = OR, NH ₂ , OH, OMe
R = C ₁ to C ₂₂ alkyl
Me = H, Na, K, Mg, Ca
m, n = 0-4
p, q = 0-45000
mean.

The crosslinkers of the formula (III) bring about crosslinking with the compounds containing amino groups via their terminal carboxyl or ester groups, with the formation of an amide function. This class of crosslinking system also includes the reaction products of monoethylenically unsaturated carboxylic acid esters with alkylenediamines and polyalkylene polyamines, for example the addition products of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and of polyethyleneimines with molar masses of, for example, 129 to 50,000 of acrylic acid or methacrylic acid or methacrylic acid or methacrylic acid 1 mol of the amine component uses at least 2 mol of the acrylic acid or methacrylic acid ester. The C ₁ to C ₆ alkyl esters of acrylic acid or methacrylic acid are preferably used as esters of monoethylenically unsaturated carboxylic acids. Acrylic acid methyl ester and acrylic acid ethyl ester are particularly preferred for the preparation of the crosslinking agents. The crosslinkers which are prepared by Michael addition of polyalkylene polyamines and ethylenically unsaturated carboxylic acids, esters, amides or anhydrides can have more than two functional groups. The number of these groups depends on the molar ratio in which the reactants are used in the Michael addition. For example, 2 to 10, preferably 2 to 8 moles of ethylenically unsaturated carboxylic acids or their derivatives can be added to one mole of a polyalkylene polyamine containing 10 nitrogen atoms in the manner of a Michael addition. At least 2 to at most 4 mol of the ethylenically unsaturated carboxylic acids or their derivatives can be added to 1 mol of polyalkylenediamines and alkylenediamines in the manner of a Michael addition.

in der X = OH, NH₂ oder OR¹ und R¹= C₁- bis C₂₂-Alkyl bedeutet, entsteht nach Art einer Michael-Addition beipielsweise ein Vernetzer der Struktur

in der X = NH₂, OH oder OR¹ und
   R¹ für C₁- bis C₂₂-Alkyl steht.In the reaction of diethylene triamine and a compound of the formula

in which X = OH, NH ₂ or OR ¹ and R ¹ = C ₁ -C ₂₂ -alkyl, a crosslinker of the structure is formed, for example, in the manner of a Michael addition

in which X = NH ₂ , OH or OR ¹ and
R ^{1 represents} C ₁ to C ₂₂ alkyl.

The secondary NH groups in the compounds of formula IV can optionally with acrylic acid, acrylamide or acrylic esters react like a Michael addition.

The compounds are preferably used as crosslinking agent of group (3) of the formula II, which contain at least 2 carboxyl groups and by reacting polyether diamines, ethylenediamine or polyalkylene polyamines available with maleic anhydride are or at least 2 ester addition-containing Michael products from polyether diamines, polyalkylene polyamines or Ethylene diamine and esters of acrylic acid or methacrylic acid with each monohydric alcohols containing 1 to 4 carbon atoms.

   worin n = 0 bis 22 bedeutet.Suitable halogen-free crosslinkers of group (4) are reaction products which are prepared by reacting dicarboxylic acid esters which are completely esterified with monohydric alcohols having 1 to 5 carbon atoms with ethyleneimine. Suitable dicarboxylic acid esters are, for example, dimethyl oxalate, diethyl oxalate, dimethyl succinate, diethyl succinate, dimethyl adipate, diethyl adipate and dimethyl glutarate. For example, the reaction of diethyl oxalate with ethyleneimine gives bis- [β- (1-aziridino) ethyl] oxalic acid amide. The dicarboxylic acid esters are reacted with ethyleneimine, for example in a molar ratio of 1 to at least 4. Reactive groups of these crosslinkers are the terminal aziridine groups. These crosslinkers can be characterized using formula V, for example:

where n = 0 to 22.

The crosslinkers described above can be used either alone or in Mix when reacting with the water-soluble specified above Condensates of basic amino acids are used. The In all cases, the crosslinking reaction is at most as far led that the resulting products are still water-soluble, e.g. should at least 10 g of the crosslinked polymer in 1 1 Dissolve water at a temperature of 20 ° C.

The condensates of basic amino acids are at least bifunctional crosslinkers preferably in aqueous solution or implemented in water-soluble organic solvents. suitable Water-soluble organic solvents are, for example, alcohols such as methanol, ethanol, isopropanol, n-propanol and butanols, Glycols such as ethylene glycol, propylene glycol or butylene glycol or Polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol and dipropylene glycol and tetrahydrofuran. The Concentration of the starting products in the solvents is in each case chosen so that reaction solutions are formed, for example Contain 5 to 50 wt .-% of cross-linked reaction products. The crosslinking is preferably carried out in aqueous solution. The temperatures during the reaction are 20 to 180, preferably 40 to 95 ° C. If the reaction temperature is above the Should be the boiling point of the solvent used, the reaction is carried out under increased pressure.

These homopolymers and copolymers based on lysine, which is also 2,6-diaminohexanoic acid or 2,6-diaminocaproic acid may differ from most common process chemicals for papermaking not only because it derived from a natural product. They unfold after the addition several different effects on paper stock, and differentiate differs from the usual process chemicals and also from those based on the natural product starch. The Polymers to be used according to the invention bring about solidification of the paper in the dry as well as in the wet state, they increase the retention of fillers and fine substances, they accelerate the dewatering of the paper stock on the paper machine screen, they increase the effectiveness of anionic retention agents, they help anionic retention aids significant drainage effect, they improve the fixation of anionic paper dyes, they are capable of undesirable anionic Oligomers and polymers, commonly known as contaminants act to fix on the paper fibers and thus from the circulating water to remove the paper machine. They also increase the absorbency of the paper.

The most surprising thing is that the polymers are based of lysine significantly increase the wet strength of the paper. Your Wet strength effect approaches or reaches, depending on the papermaking conditions, that of the commercially available wet strengthening Chemicals that are reactive synthetic Resins from the aminoplast range or based on resins of epichlorohydrin, so-called polyamide polyaminepichlorohydrin resins, hereinafter referred to as epichlorohydrin resins. Both types of resin are used for ecological and toxicological reasons no longer happy to use because the aminoplasts in and Release formaldehyde after processing and also only at low pH values in the pulp develop their effect, and because organically bound when using the epichlorohydrin resins Chlorine in the wastewater of the paper mill and in the manufactured paper cannot be avoided. The immission of organically bound Chlorine, known and measured as "Adsorbable Organic Halogen" (AOX), in the environment should be avoided if possible. Both types of resin effect the wet strength in that they with react themselves or with functional groups of paper fibers and build a waterproof network. Your reactivity is also evident in its limited shelf life. The polymers based on lysine are not reactive and their wet strength effect So far it has not been possible to explain it on paper.

Wet strength of paper is desirable when the paper is inadvertently or in contact with water contrary to its intended purpose comes and should not dissolve or after drying to show its original properties again. In such In some cases you can glue the paper additionally or alternatively, i.e. partially hydrophobic with a paper chemical and thus slow down the penetration of water into the fiber structure. It but there are many types of paper with the fastest possible Water penetration is desired, maintaining the fiber structure must stay. Examples of such papers are paper towels, Sanitary papers, paper tissues, paper napkins, Toilet paper and filter paper. It has now turned out to be surprising demonstrated that paper made with polymers based on Lysine is wet solidified, has a very high absorbency, which is higher than that which is more commercially available when used Wet strength agent is obtained, and also higher than that of the wet strength agent-free Paper with otherwise identical raw materials. There are Although known in the technical field, the absorbency of paper to increase, for example by watering or spraying the Paper web with wetting agents or hydrophilic substances, e.g. Polygykolen. However, these known methods reduce strength of the paper in the dry state. The polymeric derivatives of Natural product lysine according to the inventive method however increase the absorbency of the paper at the same time Increase in dry strength.

For many applications, the strength that the paper has is sufficient Because of its fiber composition, its filler content and of its manufacturing process. This will be in the course the growing environmental awareness and the increasing Use of waste paper, which has a far lower strength potential than fresh paper fibers, particularly blatant. But The natural strength is sufficient even when using fresh fibers often not, especially if the paper contains a lot of filler should. In such cases, the papermaker tries to Strength of its product through the addition of certain chemicals to increase. Most of the time, the paper surface is after the actual paper production with suitable chemicals, preferably treated with degraded starch. Do you want that use strength-imparting starch in the aqueous paper stock, see above it must be combined with others in a special chemical process Implemented chemicals and thus provided with cationic charges become. It has now surprisingly been shown that one too by adding polymers based on the natural product lysine according to the inventive method for aqueous paper stock the dry paper compared to the paper without solidifying Chemicals can give a significantly higher strength. You are in the use of the cationic strengths in the mass quite equivalent, but unlike the cationic ones Strengthen a number of other benefits as outlined above and described below.

Many types of paper are made by adding certain dyes dyed for aqueous paper stock suspension. It is important that the dyes as completely as possible on the fibers and fillers wind up and not get into the wastewater. This is special then a problem if with the coloristic and authenticity-relevant Reasons particularly popular anionic dyes is worked. If the wastewater with intensive dyeings is too heavily loaded or a high level of fastness to bleeding is required is, the papermaker tries to fix such dyes with fixatives to bind to the fibers and fillers, taking care must that the color and the purity of the color by the Fixatives are not affected, but still very much is often the case. Fixation poses another problem of pigments, which are particularly fast to light and bleeding Qualities are required. If not, as with traditional Paper production in an acid medium, aluminum sulfate as Fixing agents can be used, these pigments have practically no affinity. It has now been surprising demonstrated that polycations based on lysine are also capable are anionic dyes and pigments to the paper fibers bind and provide largely colorless waste water, whereby little or no impairment of the color properties of the colored paper occurs.

It is state of the art, the paper stock before Add retention and drainage agents. there it is often very high molecular weight cationic Polymers. The use of high molecular weight anionic polyacrylamides, that have certain environmental benefits for this purpose is with neutral and alkaline paper stocks, such as they become more and more popular in practice, at the same time Use of cationic fixatives bound because otherwise not the optimal retention effect of the anionic Polyacrylamide is obtained and the drainage of the Paper stock can even deteriorate. Polycations based of lysine condensates are able to effect high molecular weight anionic polyacrylamides for retention and drainage to optimize. They not only improve the retention effect of these anionic polymers, but also change the Effectiveness of the anionic polyacrylamides towards Improve drainage. They are commercially available fixatives superior in both effects. Remarkably, improve the polycations based on lysine condensates also the effectiveness of high molecular weight cationic polyacrylamides, as is commonly used in papermaking become. In addition, they also act alone as retention and drainage agents, wherein higher molecular weight polycondensates have better efficacy than low molecular weight.

As is known, accumulate in the circulation water of a paper machine anionic oligomers and polymers used in papermaking appear negatively and are therefore called contaminants become. Such contaminants affect e.g. the effectiveness of cationic retention agents and other polycations by they neutralize their positive charge and make them ineffective do. It has now been shown that the polycations Lysine based are also capable of such anionic oligomers and polymers that appear as contaminants to the paper fibers to fix and thus render harmless and from the To discharge the water system of the paper mill.

The application rates of polymers required for the effects described based on lysine condensates vary widely Differentiate limits depending on the desired effect but does not fundamentally differ from the application rates of one commercial paper chemicals used for each specific effect. To get wet hardening, one should 0.1 - 5% by weight, preferably 0.5-2% by weight, based on dry Use paper stock on polymers based on lysine. To the To increase the dry strength of the paper, you need e.g. 0.2 - 2% by weight, based on dry paper stock, of the lysine polymers. For fixation, retention and drainage effects if, for example, 0.01-1% by weight, preferably 0.02-, is used 0.2% by weight of polylysine derivatives, with the fixing of Dyes the necessary amounts up to 2%, each based on dry paper stock.

The percentages in the examples mean percent by weight, unless the context indicates otherwise. The K values according to H. Fikentscher, Cellulose-Chemie, Volume 13, 58-64 and 71-74 (1932) in aqueous solution at 25 ° C and one Concentration of 0.5 wt .-% determined.

Lysine polycondensate A:

Condensation product of lysine and aminocaproic acid in a molar ratio of 1: 1, crosslinked with 30% by weight bisglycidyl ether of a polyethylene glycol with 14 ethylene oxide units. Aqueous solution, adjusted to pH 7.0 with hydrochloric acid. The K value of the polycondensate is 64.5, the molecular weight M _w is 960,000.

Lysine polycondensate B:

Condensation product of lysine, crosslinked with 30% by weight bisglycidyl ether a polyethylene glycol with 14 ethylene oxide units. Aqueous solution, adjusted to pH 7.0 with hydrochloric acid. The K value of the polycondensate is 52.2.

Lysine polycondensate G:

Condensation product of lysine, crosslinked with 27% by weight bisglycidyl ether a polyethylene glycol with 14 ethylene oxide units. Aqueous solution, adjusted to pH 7.0 with HCl. The K value of the polycondensate is 69.

Lysine polycondensate H:

Condensation product of lysine and ε-caprolactam in the molar Ratio of 1: 1, crosslinked with 30% by weight bisglycidyl ether Polyethylene glycol with 14 ethylene oxide units. Aqueous solution, adjusted to pH 7.0 with HCl. The K value of the polycondensate is 51.0.

Compare products:

Comparative product I:

commercially available polyamide polyaminepichlorohydrin resin with 13.5% solids content (Luresin® KNU from BASF Aktiengesellschaft)

Comparative Product II:

commercially available polydiallyldimethylammonium chloride with 30% solids content (Catiofast® CS from BASF Aktiengesellschaft)

Comparative product III:

commercial dicyandiamide resin with 45% Solids content (Catiofast® FP from the company BASF Aktiengesellschaft)

Colorant a:

commercially available direct dye (C.I. Direct Blue 199) from BASF Joint stock company: Fastusol® Blau 75 L

Colorant b:

commercial pigment preparation (C.I. Pigment Blue 15.1) from BASF Public company: Fastusol® P Blau 58 L

Cationic starch I:

cationic potato starch with a degree of substitution 0.03 (Hi-Cat 110 of Roquette company)

Cationic strength II:

cationic potato starch with a degree of substitution of approx. 0.06 (Hi-Cat 160 the Roquette company)

Example 1:

To a paper stock made from unbleached pine sulfate pulp with a freeness of 25 ° SR, the amount of lysine polycondensate A or comparative product I given in Table 1 is added and the mixture is left to act for 1 minute with stirring. Then one forms 4 sheets with a sheet weight of approx. 80 g / m ² for each addition quantity with the help of the Rapid-Köthen sheet formation device. In addition, paper sheets with a sheet weight of 80 g / m ² are produced for comparison from the paper stock described in the absence of condensates or conventional paper auxiliaries. After drying using a laboratory drying cylinder, the wet tear length according to DIN 53112-2 and the suction height according to ISO 8787 are determined. The test results are shown in Table 1. They show that a similar wet strength can be achieved with the polymers based on lysine as with the products of the prior art. The absorbency of the paper increases with an increasing amount of the lysine polycondensate, while it decreases with an increasing amount of the epichlorohydrin resin. Drying at 90 ° C for 10 min; additionally aged at 130 ° C for 5 min. without wet strengthening Lysine polycondensate A Comparative product I Addition (% active substance, based on dry paper stock) 0 0.5 1 0.5 1 Basis weight (g / m ²⁾ 80.8 81.1 81.0 80.1 80.1 Drying 90 ° C Wet tear length (m) 173 645 877 577 841 Drying 130 ° C Wet tear length (m) 172 655 885 670 855 Suction height 10 min (mm) 48 59 65 59 48

Example 2:

To a paper stock made from 50 parts of bleached beech sulfite pulp and 50 parts of bleached spruce sulfite pulp with a degree of grinding of 31 ° SR, the amount of lysine polycondensate A or B given in Table 2 is added in each case. Then, for each addition quantity, formation is carried out using the Rapid-Köthen sheet-forming device 3 sheets with a sheet weight of approx. 80 g / m ² . After drying using a laboratory drying cylinder, the strengths and the suction height are determined. In addition, paper sheets with a sheet weight of 80 g / m ² are produced for comparison from the paper stock mentioned in the absence of condensates.

The test results are shown in Table 2. They show that when the polymers based on lysine are used in paper manufacture, the absorbency of the paper increases. The paper strength does not decrease, but even increases. The lysine-based polymers also act as dry strength agents. without Lysine polycondensate B Lysine polycondensate A Addition (% active substance, based on dry cellulose) 0.5 1 0.5 1 grammage g / m ² 83.6 83.4 81.8 83.1 83.3 Dry breaking length m 2916 3168 3455 3214 3329 wet breaking m 114 408 570 453 568 rel. wet strength % 4% 13% 16% 14% 17% Suction height 10 min mm 53 62 65 64 66

Example 3:

To a paper stock made of 60 parts of bleached pine sulfate pulp and 40 parts of bleached birch sulfate pulp with a freeness of 25 ° SR, the amount of the lysine polycondensates and the two cationic starches given in Table 3 are added for comparison. Then, for each addition quantity, two sheets with a sheet weight of approx. 80 g / m ^{2 are formed} using the Rapid-Köthen sheet-forming device. In addition, for comparison, sheets with a basis weight of 80 g / m ^{2 are produced} from the specified paper stock in the absence of further additives. After drying using a laboratory drying cylinder, the dry tear length and the wet tear length are determined in each case.

The test results are shown in Table 3. They show that when the polymers based on lysine are used in paper production, the same dry strength of the paper is obtained as when using cationic starches. In contrast to the cationic starches, the polylysine derivatives additionally increase the wet strength of the paper. without Cationic strength Lysinpolykondensat I II G B Amount added (% active substance, based on dry paper stock) 1 1 1 1 Dry tear length (m) 3246 3544 3447 3541 3459 Wet tear length (m) 109.3 106.8 108.8 444.3 390.4 rel. Wet strength (%) 3.4 3.0 3.2 12.5 11.3

Example 4:

To one liter of a pulp ground to a freeness of 35 ° SR with a consistency of 0.6% from 60 parts bleached Birch sulfate pulp and 40 parts of bleached pine sulfate pulp each with 40 parts of calcium carbonate the amounts of fixatives given in Table 5 or polycondensates of lysine. Then you move with the specified amount of a commercially available high molecular weight anionic Polyacrylamids (Polymin® AE 75 from BASF Aktiengesellschaft). Then the paper stock is processed in a Schopper-Riegler Deteriorated grinder tester, the time being measured in which 600 ml of water flow through the sieve of the device. The shorter the time, the more draining the chemical combination is. The white water that has passed through becomes one Turbidity measurement subjected. The clearer the white water is, the more The combination of chemicals has a stronger impact. For comparison a paper sheet is also checked, but without condensate made in the presence of anionic polyacrylamide has been. The test results are shown in Table 5.

They show that the use of lysine polycondensates in papermaking can significantly increase the retention effectiveness of high molecular weight anionic polyacrylamides, and more so than with commercially available fixatives. The results also show that the lysine polycondensates on which the process according to the invention is based give the anionic polyacrylamide a greater dewatering effect than the commercially available comparative products. Compare product Lysinpolykondensat II III B A Add fixing agent, based on dry paper pulp anionic PAM % 0 0 0.1 0.1 0.1 0.1 % 0.02 0.02 0.02 0.02 0.02 Drainage time for 600 ml turbidity: measured at sec. 40 47 37 47 31 33 588 nm 0,976 0.327 0,142 0.184 0.086 0.096

Example 5:

The procedure is as described in Example 4, but with the difference that the polylysine derivatives are compared with two commercially available cationic starches. The test results are shown in Table 5. They show that the lysine polycondensates in combination with an anionic polyacrylamide significantly accelerate the dewatering of a wood-free paper stock, while combinations of cationic starches and anionic polyacrylamide do not. It can also be seen that said combinations with lysine polycondensates have a better retention effect than combinations with cationic starches. Lysinpolykondensat Cationic strength G G H H I I II II Add fixing agent, based on dry paper stock % 0.1 0.2 0.1 0.2 0.1 0.2 0.1 0.2 anionic polyacrylamide % - 0,006 0,006 0,006 0,006 0,006 0,006 0,006 0,006 Drainage time for 600 ml sec. 31 20 20 24 21 33 33 32 30 Turbidity measured at 588 nm 3,040 0.115 0.108 0,155 0.126 0,450 0.438 0.331 0.260

Example 6:

The procedure is as described in Example 4, but with the difference that TMP (thermomechanical pulp) is used as the fiber and kaolin (China Clay) as the filler, and a high molecular weight cationic polyacrylamide (Polymin® KE 78 from BASF Aktiengesellschaft) is used as the retention agent. The test results are shown in Table 6. They show that the use of lysine polycondensates in paper production can significantly increase the dewatering and retention effectiveness of high molecular weight cationic polyacrylamides, and more so than with commercially available fixatives. Compare product Lysinpolykondensat II III B A % 0 0 0.1 0.1 0.1 0.1 Add fixi nut canonical PAM % 00:02 0.02 0.02 0.02 0.02 Eat watering time for 600 ml sec. 70 60 30 55 25 25 Turbidity: enjoyable at 588 nm 0.367 0.247 0,095 0.188 0,076 0,076

Example. 7

The procedure is as described in Example 4, but with the difference that the two cationic starches I and II are used as comparison products. The test results are shown in Table 7. They show that the use of lysine polycondesates in papermaking can significantly increase the drainage and retention effectiveness of high molecular weight cationic polyacrylamides, and more so than with commercially available cationic starches. Lysinpolykondensat Cationic strength G G H H I I II II Add fixative % 0.1 0.2 0.1 0.2 0.1 0.2 0.1 0.2 cationic PAM % - 0,004 0,004 0,004 0,004 0,004 0,004 0,004 0,004 0,004 Drainage time for 600 ml sec. 55 32 15 13 16 14 25 24 23 23 Turbidity measured at 588 nm 1,195 0.554 0.207 0.163 0,242 0.225 0.498 0.479 0.403 0.385

Example 8

The procedure is as described in Example 4, but with the difference that no high molecular weight cationic polyacrylamide is used as the retention agent, but only different amounts of the lysine polycondensates. The test results are shown in Table 8. they show that lysine polycondensates have a pronounced drainage and retention activity in papermaking even when used alone. Fabric model: 100 parts TMP, 65 ° SR ground + 20 parts China Clay X1
Fabric density: 6 g / l without Lysinpolykondensat B A Addition, based on dry paper stock % 0 0.05 0.2 0.05 0.2 Drainage time for 600 ml sec. 70 41 25 39 21 Turbidity: enjoyable at 588 nm 0.367 0.131 0.079 0.130 0,068

Example. 9

The procedure is as described in Example 4, but with the difference that cationic starches are also tested as comparative products. The test results are shown in Table 9. They show that lysine polycondensates have a significantly better drainage and retention effectiveness than cationic starches in paper production even when used alone. Lysinpolykondensat Cationic strength G G H H I I II II Add retention aid, based on dry paper stock % 0.2 0.4 0.2 0.4 0.2 0.4 0.2 0.4 Drainage time for 600 ml sec. 55 15 13 19 15 50 48 44 38 Turbidity measured at 588 nm 1,195 0,298 0.261 0.410 0,330 1,149 1,037 0,961 0.837

Example 10:

To one liter of a paper stock with a stock density of 0.6 % of 50 parts daily newspapers, 50 parts liner waste and 40 Parts of kaolin are added to the amounts given in Table 10 of sodium lignin sulfonate, cationic polyacrylamide (Polymin® KE 78 from BASF Aktiengesellschaft) and polycondensates of lysine. Then for each combination of the above Paper pulp products in a Schopper-Riegler freeness tester drained, measuring the time in which 500 ml of water flow through the sieve of the device. The shorter the time the more draining the combination of chemicals is. The Measurement results are shown in Table 11.

They show (Experiments Nos. 1-6) the known effect that the addition of sodium lignin sulfonate interferes with the good dewatering effect of the cationic polyacrylamide, even if higher amounts of the dewatering agent are used. However, if the interfering substance is bound by adding the polylysine derivatives (Experiments Nos. 8-11 and 13-16), the cationic polyacrylamide can develop its effect again. In the presence of the contaminant sodium lignin sulfonate, the polylysines alone (trials 7 and 12) hardly accelerate dewatering even in high application rates. The polylysine derivatives can therefore be used to overcome the effects of interfering substances.

Claims (8)

1. A process for the production of paper, board and cardboard by draining a paper stock in the presence of polymers with sheet formation, wherein the polymers used are crosslinked condensates which are obtainable by reaction of

   (i) homocondensates of basic amino acids, condensates of at least two basic amino acids and/or cocondensates of basic amino acids and cocondensable compounds with

   (ii) at least one crosslinking agent having at least two functional groups.
2. A process as claimed in claim 1, wherein crosslinked condensates which are obtainable with a crosslinking agent (ii) from the group consisting of the α,ω-dichloroalkanes or vicinal dichloroalkanes, epihalohydrins, bischlorohydrin ethers of polyols, bischlorohydrin ethers of polyalkylene glycols, esters of chloroformic acid, phosgene, diepoxides, polyepoxides, diisocyanates and polyisocyanates are used.
3. A process as claimed in claim 1 or 2, wherein the condensates are used in amounts of from 0.01 to 5% by weight, based on dry paper stock.
4. A process as claimed in any of claims 1 to 3, wherein the condensates are used in amounts of from 0.02 to 2% by weight, based on dry paper stock, for increasing the dry strength of the paper, for increasing the absorptivity of the paper and for fixing anionic dyes in the paper.
5. A process as claimed in any of claims 1 to 4, wherein the condensates are used in amounts of from 0.02 to 0.2% by weight for fixing interfering substances, for increasing the drainage rate of the paper stock and for increasing the retention of crill and of fillers in papermaking.
6. A process as claimed in any of claims 1 to 5, wherein the condensates are used in amounts of from 0.02 to 0.2% by weight, based on dry paper stock, in combination with synthetic anionic retention aids for increasing the drainage effect and the retention effect of the synthetic anionic retention aids.
7. A process as claimed in any of claims 1 to 6, wherein the condensates are used in amounts of from 0.02 to 0.2% by weight, based on dry paper stock, in combination with synthetic cationic retention aids for increasing the drainage effect and retention effect of the synthetic cationic retention aids.
8. The use of crosslinked condensates of basic amino acids which are obtainable by reaction of

   (i) homocondensates of basic amino acids and/or condensates of at least two basic amino acids and/or cocondensates of basic amino acids and cocondensable compounds with

   (ii)at least one crosslinking agent having at least two functional groups, in amounts of from 0.01 to 5% by weight, based on dry paper stock, as a means of increasing the wet strength, the dry strength and the absorptivity, for fixing anionic dyes and interfering substances in the paper, for increasing the drainage rate and the retention of crill and fillers and for improving the efficiency of synthetic anionic and cationic retention aids in the production of paper, board and cardboard by draining a paper stock with sheet formation.