EP0105028B1 - Process for sizing paper with anionic, hydrophobic sizing agents and cationic retention agents - Google Patents

Abstract

1. A process for sizing paper or cardboard by adding, in any order or simultaneously, to an aqueous dispersion of the fibres, which dispersion may also contain fillers, at least (A) one anionic hydrophobic sizing agent and (B) one polymeric cationic retention aid, in which process the sizing agent (A) is obtainable from (a) ketene dimers whose hydrophobic substituents have at least 5 carbon atoms, said substituents containing only carbon and hydrogen, and (b) diamines or oligoamines having 2 to 6 nitrogen atoms and 2 to 36 carbon atoms.

Description

The present invention is based on the object of providing the paper manufacturer with easily accessible and easily obtainable sizing agents which, with the use of conventional, cationic retention aids in a novel combination, are suitable for achieving good sizing in paper production from fiber suspensions.

This object is achieved according to the invention in such a way that in paper production using polymeric, cationic retention agents, compounds are used as sizing agents which contain at least two, preferably at least four long-chain, hydrophobic substituents and at least one anionic or acidic (acidic), optionally in salt form Have group.

In particular, reaction products of ketene dimers and di- or oligoamines are used according to the invention as sizing agents of this type.

US Pat. No. 2,323,938 describes reaction products of an acylethenone (obtainable, for example, from fatty acid chlorides) and a diamine, e.g. B. hexamethylenediamine, which have four long-chain, hydrophobic substituents and two acidic groups known. However, these known reaction products are used as water repellants and textile treatment agents.

A process for sizing paper is known from US Pat. No. 2,961,367, in which, however, a ketene dimer (in contrast to reaction products of ketene dimers and di- or oligoamines) is used as the anionic, hydrophobic sizing agent in the presence of a polymeric, cationic retention agent.

• (A) ein anionisches, hydrophobes Leimungsmittel und
• (B) ein polymeres, kationisches Retentionsmittel

The present invention thus relates to a process for gluing paper or cardboard, in which at least one of the aqueous, optionally filler-containing fiber suspensions

• (A) an anionic, hydrophobic sizing agent and
• (B) a polymeric, cationic retention agent

• (a) Ketendimeren, deren hydrophobe, nur Kohlenstoff und Wasserstoff enthaltenden Substituenten mindestens 5 Kohlenstoffatome aufweisen und
• (b) Di- oder Oligoaminen mit 2-6 Stickstoffatomen und 2-36 Kohlenstoffatomen erhältlich ist.

in any order or at the same time, which is characterized in that the sizing agent (A) used

• (a) ketene dimers whose hydrophobic substituents containing only carbon and hydrogen have at least 5 carbon atoms and
• (b) Di- or oligoamines with 2-6 nitrogen atoms and 2-36 carbon atoms are available.

• - die wässrigen Zusammensetzungen zur Durchführung des Papierieimungsverfahrens, die, sofern das Leimungsmittel (A) und das Retentionsmittel (B) in beliebiger Reihenfolge zur Faserstoffsuspension separat gegeben werden, neben fakultativen üblichen Zusätzen das Leimungsmittel (A) allein, das gegebenenfalls mindestens teilweise in Form von Salzen vorliegt, oder, sofern das Leimungsmittel (A) und das Retentionsmittel (B) zur Faserstoffsuspension gleichzeitig gegeben werden, sowohl das Leimüngsmittel (A) als auch das Retentionsmittel (B) neben fakultativen, üblichen Zusätzen enthalten, und
• - die Verwendung des Leimungsmittels (A) der angegebenen Art zum Leimen von Papier oder Karton.

Other He ^f indungsgegenstände form

• - The aqueous compositions for carrying out the paper sizing process, which, if the sizing agent (A) and the retention agent (B) are added separately in any order to the fiber suspension, in addition to optional conventional additives, the sizing agent (A) alone, which may be at least partially in the form of Salt is present, or if the sizing agent (A) and the retention agent (B) are added to the fiber suspension at the same time, contain both the sizing agent (A) and the retention agent (B) in addition to optional, conventional additives, and
• - The use of the sizing agent (A) of the specified type for sizing paper or cardboard.

vorliegen. Die Fähigkeit der potentiell anionischen Substituenten, in wässrigem Medium Anionen zu bilden, ist ein weiteres, wesentliches Kennzeichen des Leimungsmittels. Die Bildung von Anionen findet bei den üblicherweise bei der Papierherstellung vorliegenden pH-Werten der Faserstoffsuspensionen statt. Bei den genannten Bedingungen sind auch die kationischen Retentionsmittel (B) befähigt, Kationen zu bilden. Die Fähigkeit der Leimungsmittel bzw. der Retentionsmittel bei den Bedingungen der Papierherstellung Anionen bzw. Kationen zu bilden kann auch als anionaktiv bzw. kationaktiv bezeichnet werden. Somit können die anionischen Leimungsmittel und die kationischen Retentionsmittel auch anionaktive Leimungsmittel und kationaktive Retentionsmittel genannt werden.As an essential feature, the sizing agents (A) used according to the invention, which are obtainable from components (a) and (b), have 1 to 6, preferably 2 to 6, potentially anionic groups, which are generally in the form of acidic groups

are available. The ability of the potentially anionic substituents to form anions in an aqueous medium is another essential characteristic of the sizing agent. The formation of anions takes place at the pH values of the fiber suspensions which are usually present in papermaking. Under the conditions mentioned, the cationic retention agents (B) are also capable of forming cations. The ability of the sizing agents or the retention agents to form anions or cations under the conditions of paper production can also be described as anion-active or cation-active. Thus, the anionic sizing agents and the cationic retention agents can also be called anion-active sizing agents and cation-active retention agents.

As a further characteristic feature, the sizing agents (A), which are obtainable from components (a) and (b), have 2 to 12, preferably 4 to 12 hydrophobic, only carbon and hydrogen-containing substituents with at least 5, preferably 8 to 22, carbon atoms , e.g. B. C ₅ -C ₂ cycloalkyl or C _e -C _lo aryl, alkaryl or aralkyl radicals. Preferred hydrophobic substituents are, however, alkyl or alkenyl radicals which are generally derived from fatty acids having at least 6, preferably 8 to 22, carbon atoms. The type of linkage with which these hydrophobic substituents are bonded forms a further characteristic of the sizing agents (A). The connecting members, via which at least two of the hydrophobic groups are connected, namely preferably have 2 to 18 carbon atoms and at least 2 heteroatoms each, preferably at least 2 nitrogen atoms in the main chain. Links each having 2 to 12 carbon and two nitrogen atoms are preferred. Depending on the number of hydrophobic substituents, the sizing agents contain 1 to 5 connecting members of the type specified.

Sizing agents (A) of the type indicated which are preferably used have molecular weights of from about 1,000 to about 4,000.

As component (a), from which the sizing agent (A) is available, z. B. Dimers of the ketenes of the formulas

und

in Betracht, worin R, und R,' gleich oder voneinander verschieden sind und je einen hydrophoben Substituenten mit mindestens 5 Kohlenstoffatomen bedeuten, vorausgesetzt, dass mindestens einer der Reste R₁ und R,' mindestens 8 Kohlenstoffatome aufweist.

and

into consideration, wherein R, and R, 'are identical or different and each represent a hydrophobic substituent with at least 5 carbon atoms, provided that at least one of the radicals R ₁ and R,' has at least 8 carbon atoms.

und

worin R₂ und R₂' gleich oder voneinander verschieden sind und je Alkyl oder Alkenyl mit 5 bis 22 Kohlenstoffatomen, Cycloalkyl mit 5 bis 12 Kohlenstoffatomen oder Aryl, Alkaryl oder Aralkyl mit 6 bis 10 Kohlenstoffatomen bedeuten, vorausgesetzt, dass mindestens einer der Reste R₂ und R₂' mindestens 8 Kohlenstoffatome aufweist.Dimers of the ketenes of the formulas are preferred

and

wherein R ₂ and R ₂ 'are the same or different and are each alkyl or alkenyl having 5 to 22 carbon atoms, cycloalkyl having 5 to 12 carbon atoms or aryl, alkaryl or aralkyl having 6 to 10 carbon atoms, provided that at least one of the radicals R ₂ and R ₂ 'has at least 8 carbon atoms.

und

wobei sich die Ketene jeweils von einer ungesättigten oder gesättigten Fettsäure mit mindestens 6, vorzugsweise 8 bis 22 Kohlenstoffatomen ableiten und R₃ und R₃' gleich oder voneinander verschieden sind, vorausgesetzt, dass mindestens einer der Reste R₃ und R₃' sich von einer Fettsäure ableitet, die mindestens 8 Kohlenstoffatome aufweist.Of primary interest are dimers of the ketenes of the formulas

and

wherein the ketenes are each derived from an unsaturated or saturated fatty acid having at least 6, preferably 8 to 22 carbon atoms and R ₃ and R ₃ 'are the same or different, provided that at least one of the radicals R ₃ and R ₃ ' is different from one Derives fatty acid that has at least 8 carbon atoms.

In the definitions of R ₂ and R ₂ ^, in the formulas (3) and (4) as representatives of C _S -C ₁₂ cycloalkyl z. B. cyclopentyl, cyclododecyl and especially cyclohexyl and as representatives of C ₆ -C ₁₀ aryl, alkaryl or aralkyl z. B. naphthyl, tolyl, xylyl, phenylethyl and especially called β-naphthyl, benzyl and phenyl.

The unsaturated or saturated C ₆ -C ₂₂ , preferably C ₈ -C ₂₂ fatty acids from which the ketenes of the formulas (5) and (6) are derived are, for. B. capronic, preferably caprylic, capric and arachic acid, especially lauric, myristic, palmitic, stearic and behenic acid or myristoleic, palmitoleic, elaeostearic, clupanodonic acid, especially oil, elaidic, erucic , Linoleic and linolenic acid. Lauric, palmitic, stearic, oleic and behenic acids are of particular importance here. Stearic acid is the focus of interest and is mainly used in combination with the other last-mentioned fatty acids. Ketenes which are derived from industrial mixtures of the saturated and / or unsaturated fatty acids mentioned are particularly preferred.

und

wobei sich die Ketene jeweils von Laurin-, Palmitin-, Stearin-, Oel- oder Behensäure oder deren Gemischen ableiten und R₄ und R₄' gleich oder voneinander verschieden sind, im Vordergrund des Interesses.Thus dimers of the ketenes of the formulas

and

where the ketenes are each derived from lauric, palmitic, stearic, oleic or behenic acid or mixtures thereof and R ₄ and R ₄ 'are the same or different from one another, in the foreground of interest.

The ketene dimers of the type specified are known per se and, for. B. described in U.S. Patent 4,317,756. Their manufacture, e.g. B. from the corresponding acid halides, especially fatty acid chlorides, and strong tertiary bases, especially trialkylamines, z. B. disclosed in U.S. Patent 2,383,863.

In the aforementioned US patent 4317756, the ketene dimers, wherein R ₁ and R ₁ 'in formulas (1) and (2) are the same, are represented by the formula

worin R, die angegebene Bedeutung hat, angegeben. Es kommen aber auch cyclische Darstellungen für Ketendimere in Betracht, die der Formel

entsprechen, worin R_I und R_I' gleich oder voneinander verschieden sind und die angegebene Bedeutung haben.

where R, has the meaning given. However, cyclic representations for ketene dimers are also possible, that of the formula

correspond in which R _I and R _I 'are the same or different and have the meaning given.

Component (b) from which the sizing agent (A) is obtainable are aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic di- or oligoamines with 2 to 6 nitrogen atoms and 2 to 36 carbon atoms. The oligoamines are primarily aliphatic amines, in particular polyalkylene polyamines with a maximum of 6 nitrogen atoms and 2 or 3 carbon atoms in each alkylene bridge member. In the case of the diamines, on the other hand, aromatic or araliphatic bridge members, preferably having 6 to 16 carbon atoms or heterocyclic bridge members, preferably the piperazine series, as well as aliphatic bridge members having preferably 2 to 8 carbon atoms or cycloaliphatic bridge members having preferably 5 to 12 carbon atoms are possible between the two nitrogen atoms .

Accordingly, preferred di- or oligoamines correspond to the formula

worin A, Alkylen, Hydroxyalkylen, Alkenylen oder Cycloalkylen mit höchstens 12 Kohlenstoffatomen, einen Alkaryl- oder Arylrest einer der Formel

oder

oder Naphthylen, einen heterocyclischen Rest der Formel

oder A_t, sofern Oligoamine vorliegen, einen aliphatischen Rest der Formel

D₁ Wasserstoff oder einen sich von Fettsäuren mit 8 bis 22 Kohlenstoffatomen ableitenden Alkyl- oder Alkenylrest, E₁ und E₁' je Aethylen oder n-Propylen, n₁, n₂, n₃ und n₄ je 1, 2 oder 3 und m eine ganze Zahl von 1 bis 4 bedeuten.

wherein A, alkylene, hydroxyalkylene, alkenylene or cycloalkylene with at most 12 carbon atoms, an alkaryl or aryl radical of one of the formula

or

or naphthylene, a heterocyclic radical of the formula

or A _t , if oligoamines are present, an aliphatic radical of the formula

D _{1 is} hydrogen or an alkyl or alkenyl radical derived from fatty acids having 8 to 22 carbon atoms, E ₁ and E ₁ 'per ethylene or n-propylene, n ₁ , n ₂ , n ₃ and n ₄ each 1, 2 or 3 and m is an integer from 1 to 4.

If A _{1 is} alkylene, hydroxyalkylene or alkenylene, it is a matter of both branched and straight-chain bridge members. Alkenylene radicals generally have 3 to 8 carbon atoms and 3 or 2 double bonds or preferably only one double bond. Alkylene is preferred over alkenylene and generally has 2 to 9, in particular 2 to 6, carbon atoms. Alkylene radicals can be unsubstituted or substituted by preferably at most 2 hydroxyl groups, in particular only one hydroxyl group. Such hydroxyalkylene residues are generally straight-chain. Cyclodecylene, cyclododecylene and especially cyclopentylene and in particular cyclohexylene may be mentioned as representatives of cycloalkylene radicals. If D _{1 is} an alkyl or alkenyl radical, it is preferably derived from the above-mentioned C ₆ -C _22, preferably C ₈ -C ₂₂ fatty acids. D ₁ preferably represents alkyl or alkenyl radicals only insofar as A _{1 is} alkylene. Ethylene is the meaning of E ₁ and E ₁ ' prefers. Preferably, n and n ₂ each represent 1 or 2 and n ₃ and n ₄ each represent 1. Preferred representatives of the formula (9.1) are toluylene and especially aflem xylylene and phenylene and the formula (9.2) preferably represents diphenylene ether.

worin A₂ unsubstituiertes, geradkettiges oder verzweigtes Alkylen oder durch Hydroxy substituiertes geradkettiges Alkylen mit 2 bis 9 Kohlenstoffatomen, Cyclopentylen, Cyclohexylen, Phenylen, Toluylen, Xylylen, Diphenylenäther, oder

D₂ Wasserstoff, oder sofern A₂ Alkylen ist, D₂ auch einen sich von einer Fettsäure mit 8 bis 22 Kohlenstoffatomen ableitenden Alkyl- oder Alkenylrest und m eine ganze Zahl von 1 bis 4 bedeuten, und insbesondere der Formel

worin A₃ unsubstituiertes oder durch höchstens einen Methyl- oder Hydroxylrest substituiertes, geradkettiges Alkylen mit insgesamt 2 bis 6 Kohlenstoffatomen, Cyclohexylen, Phenylen, Diphenylenäther, Xylylen oder den Rest der Formel (10.1) bedeutet, D₃ Wasserstoff, oder, sofern A₃ Alkylen ist, D₃ auch einen Alkyl- oder Alkenylrest bedeutet, der sich von Laurin-, Palmitin-, Stearin-, Oel- oder Behensäure oder deren Gemischen ableitet.Thus di- or oligoamines, which are of primary interest, correspond to the formula

wherein A _{2 is} unsubstituted, straight-chain or branched alkylene or straight-chain alkylene substituted by hydroxy with 2 to 9 carbon atoms, cyclopentylene, cyclohexylene, phenylene, tolylene, xylylene, diphenylene ether, or

D _{2 is} hydrogen, or if A _{2 is} alkylene, D _{2 is} also an alkyl or alkenyl radical derived from a fatty acid having 8 to 22 carbon atoms and m is an integer from 1 to 4, and in particular of the formula

wherein A _{3 is} unsubstituted or substituted by at most one methyl or hydroxyl radical, straight-chain alkylene with a total of 2 to 6 carbon atoms, cyclohexylene, phenylene, diphenylene ether, xylylene or the rest of the formula (10.1), D _{3 is} hydrogen or, if A _{3 is} alkylene D _{3 is} also an alkyl or alkenyl radical which is derived from lauric, palmitic, stearic, oleic or behenic acid or mixtures thereof.

wobei Formel (12) zutrifft, sofern Diamine als Ausgangskomponente (a) und Formel (13) zutrifft, sofern Oligoamine als Ausgangskomponente (a) eingesetzt werden, und in Formeln (12) und (13) A_o Alkylen, Hydroxyalkylen, Alkenylen oder Cycloalkylen mit höchstens 12 Kohlenstoffatomen, einen Alkaryl- oder Arylrest der Formeln (9.1) oder (9.2) oder Naphthylen, oder einen heterocyclischen Rest der Formel (9.3), E, und E₁' je Aethylen oder n-Propylen, D, Wasserstoff oder einen sich von Fettsäuren mit 8 bis 12 Kohlenstoffatomen ableitenden Alkyl- oder Alkenylrest und R, und R₁' gleich oder voneinander verschieden sind und je einen hydrophoben Substituenten mit mindestens 5 Kohlenstoffatomen bedeutet, vorausgesetzt, dass mindestens einer der Reste R, und R₁' mindestens 8 Kohlenstoffatome aufweist. Falls die Leimungsmittel der Formel (12) oder (13) als Salze vorliegen, so ist das Wasserstoffatom in den Gruppierungen

mindestens teilweise durch das Kation des entsprechenden Salzes ersetzt.The sizing agents (A) used according to the invention are characterized in that they are obtainable from the above-mentioned ketene dimers as component (a) and di- to oligoamines as component (b). Provided that dimers of the ketenes of the formulas (1) and (2) or ketene dimers of the formula (1.1) or (1.2) are used as component (a) and di- or oligoamines of the formula (9) are used as component (b), the sizing agents (A) or their salts correspond to one of the probable formulas

where formula (12) applies if diamines are used as starting component (a) and formula (13) applies if oligoamines are used as starting component (a), and in formulas (12) and (13) A _o alkylene, hydroxyalkylene, alkenylene or cycloalkylene with a maximum of 12 carbon atoms, an alkaryl or aryl radical of the formulas (9.1) or (9.2) or naphthylene, or a heterocyclic radical of the formula (9.3), E, and E ₁ 'per ethylene or n-propylene, D, hydrogen or one alkyl or alkenyl radicals derived from fatty acids with 8 to 12 carbon atoms and R, and R ₁ 'are identical or different and each represents a hydrophobic substituent with at least 5 carbon atoms, provided that at least one of the radicals R ₁ and R ₁ ' is at least Has 8 carbon atoms. If the sizing agents of the formula (12) or (13) are present as salts, the hydrogen atom is in the groupings

at least partially replaced by the cation of the corresponding salt.

• (a) ein Dimer eines Ketens der Formeln (1) und (2) mit
• (b) einem Diamin der Formel
  
  oder einem Oligoamin der Formel
  
  worin A_o, D_1, E_1, E; und m die angegebenen Bedeutungen haben, miteinander umsetzt.

To prepare the reaction products of the formula (12) or (13), the procedure is such that

• (a) a dimer of a ketene of the formulas (1) and (2) with
• (b) a diamine of the formula
  
  or an oligoamine of the formula
  
  wherein A _o , D _1, E _1, E; and m have the meanings given, implemented with one another.

In this production process, preferably 1 to 1.1 equivalents, in particular 1.0 equivalent, per mole of component (a) are used per mole of component (b), the reaction generally being in the melt or preferably in at least one organic solvent, ie. H. in a single solvent or in a solvent mixture, at preferred temperatures of about 10 to about 140 ° C.

The solvents used must be each of the starting components (a) and (b) as well as the end product, i.e. H. be inert to the reaction products from (a) and (b). As a solvent such. B. optionally halogenated hydrocarbons into consideration, which have a boiling point of at most 140 ° C, preferably between about 80 ° and about 140 ° C, such as benzene, especially toluene, chlorobenzene, o-, m- and p-xylene, a technical Xylene mixture or mixtures of the hydrocarbons mentioned are preferred. however, lower boiling, e.g. B. boiling at about 40 to about 80 ° C, preferably halogenated hydrocarbons, for example dichloroethane, carbon tetrachloride or especially chloroform are preferred. It is particularly expedient to carry out the reaction at the reflux temperature of the solvent of the type specified in each case.

Before they are used as component (A) in the paper sizing process according to the invention, the sizing agents generally do not need to be cleaned and recrystallized after production, but can generally be used directly.

der Umsetzungsprodukte der Formel (12) oder (13) eingesetzt. Die somit als Salze vorliegenden Umsetzungsprodukte entsprechen der Formel (12) oder (13), wobei die aciden Gruppierungen mindestens teilweise in die entsprechenden Anionen

übergeführt werden, deren negative ladung^S durch die entsprechenden Amin-, Ammonium- oder Alkalimetall-Kationen neutralisiert wird.Especially when the sizing agent (A) and the retention agent (B) are added separately (in any order) to the fiber suspension in the process according to the invention for sizing paper or cardboard, it is expedient to use the sizing agent partially in salt form. If necessary, such salts can be obtained by, after the reaction of components (a) and (b) has ended, the reaction products obtained by adding, inter alia, an alkylamine or alkanolamine having a total of at most 6 carbon atoms, for. B. trimethylamine, triethylamine, monoethanolamine, diethanolamine, especially by adding ammonia or an alkali metal hydroxide, for example potassium or especially sodium hydroxide, usually in an aqueous medium at room temperature (about 15 to about 25 ° C) in the corresponding salts, if appropriate at least partially transferred. Advantageously, an alkali metal hydroxide, e.g. As potassium or especially sodium hydroxide or especially ammonia usually used in the form of their diluted, about 1 to 10 weight percent aqueous solution. As a rule, it is expedient to use at most 2 mol, especially at most 1 mol, preferably 0.1 to 0.9, in particular 0.1 to 0.7 mol of ammonia or alkali metal hydroxide per group of the formula present

of the reaction products of the formula (12) or (13). The reaction products thus present as salts correspond to the formula (12) or (13), the acidic groups at least partially into the corresponding anions

are transferred, the negative charge ^S of which is neutralized by the corresponding amine, ammonium or alkali metal cations.

In addition to the new, previously described, anionic or acidic sizing agent (A), the paper sizing process according to the invention always uses a polymeric, cationic retention agent (B) which generally has a molecular weight of at least 1,000, especially at least about 2,500, preferably from about 2,000 to about 2,000,000, more preferably from about 5,000 to about 2,000,000. Retention agents with molecular weights in the range of 10,000 to 100,000 are particularly preferred. In principle, any commercially available retention agent can be considered for use in the process according to the invention.

Examples of conventional retention agents (B) which are particularly suitable for use together with the sizing agent (A) in the paper sizing process according to the invention are polyalkyleneimines, epihalohydrin adducts of reaction products from polyalkylene polyamides _. NEN and from aliphatic dicarboxylic acids or from reaction products from polyalkylene polyamines, from dicyandiamide and optionally from unesterified or esterified with alkanols, organic dicarboxylic acids. Reaction products from dicyandiamide, from formaldehyde, from ammonium salts of strong inorganic acids and from alkylenediamines or polyalkylene polyamines, cationically modified starches or carbohydrates from locust bean or guar gum, copolymers based on polyamide amines and reaction products from epihalohydrins and from polymerized diallylamines.

Preferred epichlorohydrin adducts of reaction products of polyalkylene polyamines and aliphatic dicarboxylic acids are r. B. in British Patent 865 727, epichlorohydrin adducts from reaction products of dicyandiamide and diethylenetriamine or triethylenetetramine z. B. in German Offenlegungsschrift 2710061 and in British Patent 1 125486, epichlorohydrin adducts of reaction products of diethylenetriamine, dicyandiamide and unesterified or preferably esterified with lower alkanols, especially dimethyl adipate, dicarboxylic acids. B. in British Patent 1 125 486 and reaction products of dicyandiamide, formaldehyde, ammonium salts of strong organic acids and from ethylenediamine or triethyl tetramine z. B. described in US Pat. No. 3,491,064. Preferred cationically modified starches and carbohydrates from locust bean or guar gum are alkylene oxide adducts of these starches or carbohydrates, the alkylene oxide used having 2 or 3 carbon atoms in the alkylene radical and quaternary ammonium groups. Copolymers based on polyamide amines have molecular weights of 10 ³ to 10 ⁵ , preferably 10 ³ to 10 ° and are, for. B. from aliphatic, saturated dicarboxylic acids having 2 to 10, preferably 3 to 6 carbon atoms, especially adipic acid, and polyalkylene polyamines, for. B. polypropylene and polyethylene polyamine, especially dimethylaminohydroxypropyl-diethylenetriamine, available. You are e.g. B. in CTFA Cosmetic Ingredient Dictionary, 3rd edition 1982, the Cosmetic Toiletry and Fragrance Association. Reaction products from epihalohydrins and polymerized diallylamines preferably have molecular weights of 1,000 to 2,000 and are e.g. For example, see U.S. Patents 3,700,623 and 4,279,794.

As retention agents (B), which are in the foreground of interest for use together with the sizing agents (A) in the paper sizing process according to the invention, is a maize or potato starch modified with a propylene oxide containing quaternary ammonium groups, the 25% strength of which is suspended in distilled water at 20 ° C has a pH of 4.2 to 4.6, a polyethyleneimine which has a molecular weight of 10,000 to 100,000, an epichlorohydrin adduct of a reaction product of triethylene tetramine and dicyandiamide, an epichlorohydrin adduct of a reaction product of diethylene triamine, dicyandiamide and dimethyl adipate , a reaction product of dicyandiamide, formaldehyde, ammonium chloride and ethylenediamine, an epichlorohydrin adduct of a poly-N-methyldiallylamine and a copolymer of adipic acid and dimethylamino-hydroxypropyldiethylenetriamine.

According to the process, 0.02 to 3, preferably 0.1 to 3, in particular 0.2 to 0.8, percent by weight of the sizing agent (A) and 0.02 to 3, preferably 0.1 to 3, in particular 0.2, are generally used up to 0.4 percent by weight of the retention agent (B), based in each case on the dry matter of (A) and (B) and on the solids content of the fiber suspension. 0.02 to less than 0.1 percent by weight of the sizing agent (A) and the retention agent (B) are sufficient only for the so-called "size press control", which cannot be determined with conventional sizing tests (see, for example, the article "Control and understanding of size press pickup by DR Dill in the journal TAPPI (Proceedings of the Technical Association of the Pulp and Paper Industry), Volume 57, No. 1 of January 1974, pages 97 to 100).

The fiber suspension, to which the sizing agents (A) and the retention agents (B) are added, generally has a solids content of 0.1 to 5, preferably 0.3 to 3, in particular 0.3 to 1 percent by weight and a Schopper- Riegler freeness from 20 to 60 °, preferably 20 to 45 °, in particular 25 to 35 °. It usually contains pulp, especially those made of softwood, e.g. B. pine wood, or hardwood, d. H. Hardwood z. B. beech wood, which by conventional methods, for. B. the sulfite or especially the sulfate process. In addition, the fiber suspension may contain groundwood. Waste paper containing alum can also be contained in the fiber suspension. Also pulp suspensions made according to the so-called CMP or CTMP process (Chemimechanical and chemithermomechanical pulping processes, see e.g. article «Developments in refiner mechanical pulping by SA Collicutt and co-workers in TAPPI, Volume 64, No. 6 from June 1981 , Pages 57 to 61) come into consideration.

The fiber suspension can also contain organic or mineral fillers. As organic fillers come u. a. synthetic pigments, e.g. B. polycondensation products of urea or melamine and formaldehyde with large specific surfaces, which are in highly dispersed form and u. a. in British patents 1,043,937 and 1,318,244 are described as mineral fillers and. a. Montmorillonite, titanium dioxide, calcium sulfate and especially talc, kaolin and / or chalk (calcium carbonate). As a rule, the fibrous suspension contains 0 to 40, preferably 5 to 25, in particular 15 to 20 percent by weight, based on the solids content of the fibrous suspension, of dry matter of the fillers of the type specified.

The pH of the fiber suspension can be in a wide range, z. B. Values from 3.5 to about 10 may be present.

When adding z. B. Calcium carbonate, alkaline fiber suspensions are obtained with a pH of about 7 to about 9, preferably 7.5 to 8.5. Acidic fiber suspensions with a pH of 3.5 to 7, preferably 5 to 7, in particular 5 to 6, can in the absence of calcium carbonate by adding acids, e.g. B. sulfuric or formic acid or especially z. B. latent acidic sulfates such as aluminum sulfate (alum) can be obtained.

Fibrous suspensions that contain no filler can be used in a wide pH range of e.g. B. 3.5 to 10 are present. Preferred are fiber suspensions, optionally by adding chalk have a pH of about 7 to about 9 and are advantageous insofar as possible signs of corrosion on the sensitive paper machines are excluded.

The fibrous suspension can also contain additives such as. B. starch or its degradation products. which increase the fiber / fiber or fiber / filler bond.

High molecular weight polymers of the acrylic acid series, e.g. B. polyacrylamides with molecular weights above 1,000,000 can be added to the fiber suspensions as an aid to retain the finest cellulose fiber particles, with minimal amounts of about 0.005 to 0.02 percent by weight, based on the dry matter of the high polymer and the solids content of the fiber suspensions, being sufficient .

In the process according to the invention, the fibrous suspension is processed further in a manner known per se on sheet formers or, preferably, continuously on paper machines of conventional design to give paper or cardboard. After drying at about 100 to 140 ° C for about 0.5 to 10 minutes, papers with a variable basis weight of z. B. 50 to 200 g / m ² obtained.

As mentioned at the beginning, the aqueous composition for carrying out the paper sizing process according to the invention contains, in addition to optional customary additives, the sizing agent (A), provided that the sizing agent (A) and the retention agent (B) are added separately to the fiber suspension. In this case, the preparation preferably contains the sizing agent partly in the form of its salts (obtained using, for example, ammonia, an alkyl- or alkanolamine or an alkali metal hydroxide of the type mentioned in the ratios given above). In general, such compositions contain 5 to 30, preferably 5 to 20 percent by weight of dry matter of the sizing agent, which is partially in salt form, based on the weight of the aqueous composition.

• (A) 2 bis 40, vorzugsweise 5 bis 30, insbesondere 5 bis 10 Gewichtsprozent Leimungsmittel (berechnet als Trockensubstanz), bezogen auf das Gewicht der wässrigen Zusammensetzung,
• (B) 0,1 bis 20, vorzugsweise 0,5 bis 10, insbesondere 3 bis 8 Gewichtsprozent Retentionsmittel (berechnet als Trockensubstanz), bezogen auf die wässrige Zusammensetzung.

On the other hand, the aqueous composition contains, in addition to the optional optional additives, provided the sizing agent (A) and the retention agent (B) are added to the fiber suspension at the same time.

• (A) 2 to 40, preferably 5 to 30, in particular 5 to 10 percent by weight of sizing agent (calculated as dry substance), based on the weight of the aqueous composition,
• (B) 0.1 to 20, preferably 0.5 to 10, in particular 3 to 8 percent by weight retention aid (calculated as dry matter), based on the aqueous composition.

The aqueous compositions of the type mentioned may contain surface-active compounds, e.g. B. dispersants or further emulsifiers and / or water-soluble organic solvents. As dispersants and emulsifiers come, for. B. conventional lignin sulfonates, ethylene oxide adducts of alkylphenols, fatty amines, fatty alcohols or fatty acids, fatty acid esters of polyhydric alcohols, substituted benzimidazoles or condensation products of aromatic sulfonic acids and formaldehyde into consideration. Other surface-active compounds are preferably the anionic surfactants, especially sulfate surfactants, e.g. B. diethanolamine lauryl sulfate or ethoxylated lauryl sulfates. Possible water-soluble, organic solvents are aliphatic ethers with 1 to 10 carbon atoms, e.g. B. dioxane, methylene glycol n-butyl ether or diethylene glycol monobutyl ether or alcohols with 1 to 4 carbon atoms, e.g. B. isopropanol, ethanol or methanol.

The compositions are prepared in a conventional manner by combining the sizing agent (A) together with the retention agent (B) or the sizing agent (A) e.g. B. partially in the form of its salt alone either in the molten state or preferably in the solid state, in particular in powdered form, usually in the presence of glass beads and, if necessary, emulsifiers (in the case of sizing agents in the molten state) or dispersants (in the case of sizing agents in powder form) ) stirred at a maximum of 90 ° C, preferably about 50 to 85 ° C for emulsions, in particular at about 15 to 25 ° C for dispersions, storage-stable, homogeneous emulsions or preferably dispersions being obtained. Since the sizing agents together with the retention aids or the sizing agents which are partially present as salts are generally self-dispersing or self-emulsifying, the use of dispersing agents or emulsifying agents is generally not necessary. This also applies to the optional addition of solvents and / or surfactants, which are only used if the dispersions or emulsions have insufficient storage stability.

As an advantage of the method according to the invention, it should be mentioned that fiber suspensions of the most varied types can be processed in a simple manner with relatively small amounts of sizing and retention agent into paper, which has good sizing properties (ink floating time and above all water absorption according to Cobb). The paper sized according to the process has good mechanical properties, ie good strengths, in particular good tear strength. Good reproducibility of the process is guaranteed. In particular, pulp suspensions containing wood pulp or waste paper can be processed. The compatibility of the sizing agent used according to the invention with a wide variety of fillers and their additives, such as. B. kaolin or alum in acidic areas of the fiber suspensions is advantageous. The sizing agents also have advantageous compatibility with optical brighteners. In addition, the degree of whiteness of the glued paper is not significantly influenced by the gluing and can even u. U. be improved. Above all, the surprisingly high storage stability of the sizing agent dispersions of the type indicated is of great advantage. This advantageous storage stability applies both to dispersions of sizing agents (A) alone and to dispersions of mixtures of sizing agents (A) and retention aids (B). In particular, it is much better for dispersions of reaction products from components (a) and (b) than sizing agents (A) or their mixtures with retention agents (B) than for dispersions of component (a) alone or their mixtures with retention agents (B ).

The parts and percentages given in the following exemplary embodiments relate to the weight.

Manufacturing examples example 1

und

werden in 300 Teilen Chloroform gelöst. Innerhalb von 5 Minuten werden 5,2 Teile (0,05 Mol) Diäthylentriamin zur Ketendimerlösung gegeben, wobei sich die Rückflusstemperatur von ca. 62 °C des Reaktionsgemisches von selbst einstellt. Anschliessend wird das Reaktionsgemisch während 2,5 Stunden bei dieser Temperatur gehalten. Nach dem Entfernen des Chloroforms unter vermindertem Druck erhält man als Destillationsrückstand 80,2 Teile (100 % der Theorie) des rohen Umsetzungsproduktes der Formel

q=13 und q'=16 oderq=14 und q'=1575 parts (0.15 mol) of the dimer from the ketenes of the formulas

and

are dissolved in 300 parts of chloroform. 5.2 parts (0.05 mol) of diethylenetriamine are added to the ketene dimer solution over the course of 5 minutes, the reflux temperature of approximately 62 ° C. of the reaction mixture being established automatically. The reaction mixture is then kept at this temperature for 2.5 hours. After removal of the chloroform under reduced pressure, 80.2 parts (100% of theory) of the crude reaction product of the formula are obtained as the distillation residue

q = 13 and q '= 16 or q = 14 and q' = 15

• Schmelzpunkt : 70-75 °C.
• Elementaranalyse :
  

The crude reaction product is recrystallized from ethanol for analysis purposes. The recrystallized product is in the form of a crystalline, colorless powder. It is free of unreacted ketene dimer due to the results of the infrared spectrum and the liquid chromatogram.

• Melting point: 70-75 ° C.
• Elemental analysis:
  

Example 2

The procedure described in Example 1 is followed, except that 51 parts (0.1 mol) of the dimer from the ketenes of the formula (16) and (17) and 3.6 parts (0.025 mol) of triethylenetetramine are used. 54.6 parts (100% of theory) of the crude reaction product of the formula are obtained

q und q' wie in Formel (18) angegeben.

q and q 'as indicated in formula (18).

• Schmelzpunkt : 56-61 °C
• Elementaranalyse :
  

The recrystallized product is also in the form of a crystalline, colorless powder which is free from unreacted ketene dimer.

• Melting point: 56-61 ° C
• Elemental analysis:
  

Example 3

q und q' wie in Formel (18) angegeben.The procedure described in Example 1 is followed, except that 35.4 parts (0.07 mol) of the dimer from the ketenes of the formulas (16) and (17) and 2.7 parts (0.014 mol) of tetraethylene pentamine are used. 38.1 parts (100% of theory) of the crude reaction product of the formula are obtained

q and q 'as indicated in formula (18).

• Schmelzpunkt : 49-55 °C
• Elementaranalyse :
  

The crude product is recrystallized from acetone for analysis purposes. The recrystallized product is in the form of a colorless powder. It is also free of unreacted ketene dimer.

• Melting point: 49-55 ° C
• Elemental analysis:
  

Example 4

The procedure described in Example 1 is followed, except that 35.4 parts (0.07 mol) of the dimer from the ketenes of the formulas (16) and (17) and 2.8 parts (0.012 mol) of pentaethylene hexamine are used. 38.2 parts (100% of theory) of the crude reaction product of the formula are obtained

q und q' wie in Formel (18) angegeben.

q and q 'as indicated in formula (18).

• Schmelzpunkt : 49-51 °C
• Elementaranalyse :
  

The crude product is recrystallized from acetone for analysis purposes. The recrystallized product is in the form of a colorless powder. It is also free of unreacted ketene dimer.

• Melting point: 49-51 ° C
• Elemental analysis:
  

Example 5

q und q' wie in Formel (18) angegeben.The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 1.5 parts (0.025 mol) of 1,2-diaminoethane are used. 26.8 parts are obtained (100% of theory) of the raw reaction product of the formula

q and q 'as indicated in formula (18).

• Schmelzpunkt : 110-113°C
• Elementaranalyse :
  

The crude product is recrystallized from acetone for analysis purposes. The recrystallized product is in the form of a colorless powder. It is also free of unreacted ketene dimer.

• Melting point: 110-113 ° C
• Elemental analysis:
  

Example 6

The procedure is as described in Example 1, but 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 1.8 parts (0.025 mol) of 1,3-diaminopropane are used. 27.1 parts (100% of theory) of the crude reaction product of the formula are obtained

q und q' wie in Formel (18) angegeben.

q and q 'as indicated in formula (18).

• Schmelzpunkt: 89-91 °C
• Elementaranalyse :
  

The crude product is recrystallized from acetone for analysis purposes. The recrystallized product is in the form of a colorless powder. It is also free of unreacted ketene dimer.

• Melting point: 89-91 ° C
• Elemental analysis:
  

Example 7

q und q' wie in Formel (18) angegeben.The procedure is as described in Example 1, but 35.4 parts (0.07 mol) of the dimer from the ketenes of the formulas (16) and (17) and 4.1 parts (0.035 mol) of 1,6-diaminohexane are used. 39.5 parts (100% of theory) of the crude reaction product of the formula are obtained

q and q 'as indicated in formula (18).

• Schmelzpunkt : 96-98 °C
• Elementaranalyse :
  

The crude product is recrystallized from acetone for analysis purposes. The product recrystallized from this is in the form of a colorless powder. It is also free of unreacted ketene dimer.

• Melting point: 96-98 ° C
• Elemental analysis:
  

Example 8

The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 2.2 parts (0.017 mol) of bis (3-aminopropyte) are used. amine a. 27.5 parts (100% of theory) of the crude reaction product of the formula are obtained

q und q' wie in Formel (18) angegeben.

q and q 'as indicated in formula (18).

• Schmelzpunkt : 68-70 °C
• Elementaranalyse :
  

The crude product is recrystallized from acetone for analysis purposes. The recrystallized product is in the form of a colorless powder. It is also free of unreacted ketene dimer.

• Melting point: 68-70 ° C
• Elemental analysis:
  

Example 9

The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 2.2 parts (0.013 mol) of 1,2-bis (3 -aminopropylamino) -ethane. 27.5 parts (100% of theory) of the crude reaction product of the formula are obtained

q und q' wie in Formel (18) angegeben.

q and q 'as indicated in formula (18).

• Schmelzpunkt : 52-55 °C
• Elementaranalyse :
  

The crude product is recrystallized from acetone for analysis purposes. The recrystallized product is in the form of a colorless powder. It is also free of unreacted ketene dimer.

• Melting point: 52-55 ° C
• Elemental analysis:
  

Example 10

• q und q' wie in Formel (18) angegeben.
• Q₁ = Gemisch aus C₁₆-_, C₁₇- und C₁₈-Alkyl.

The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 8.2 parts (approx. 0.025 mol) of an industrial mixture of N are used - (3-Aminopropyl) hexadecyl, heptadecyl and octadecyl amine. 33.5 parts (100% of theory) of the crude reaction product mixture of the formula are obtained

• q and q 'as indicated in formula (18).
• Q ₁ = mixture of C _{16 ,} C ₁₇ and C ₁₈ alkyl.

• Schmelzpunkt : 69-72 °C.

The crude product mixture is recrystallized from acetone. The recrystallized product mixture is in the form of a yellowish powder. It is also free of unreacted ketene dimer.

• Melting point: 69-72 ° C.

Example 11

• q und q' wie in Formel (18) angegeben.
• Q₂ = Gemisch aus C₂₀- und C₂₂-Alkyl.

The procedure is as described in Example 1, but 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 10.9 parts (approx. 0.025 mol) of an industrial mixture of N- ( 3-aminopropyl) eicosyl and docosylamine. 36.2 parts (100% of theory) of the crude reaction product mixture of the formula are obtained

• q and q 'as indicated in formula (18).
• Q ₂ = mixture of C ₂₀ and C ₂₂ alkyl.

The crude product mixture is recrystallized from acetone. The recrystallized product mixture is in the form of a yellowish powder. It is also free of unreacted ketene dimer.

• Melting point: 48-52 ° C.

Example 12 -

The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 2.7 parts (0.025 mol) of 1,3-diaminobenzene are used. 28.0 parts (100% of theory) of the crude reaction product of the formula are obtained

q und q' wie in Formel (18) angegeben.

q and q 'as indicated in formula (18).

• Schmelzpunkt : 52-55 °C,
• Elementaranalyse :
  

The crude product is recrystallized from acetone for analysis purposes. The recrystallized product is in the form of a colorless powder. It is also free of unreacted ketene dimer.

• Melting point: 52-55 ° C,
• Elemental analysis:
  

Example 13

q und q' wie in Formel (18) angegeben.The procedure is as described in Example 1, but 35.4 parts (0.07 mol) of the dimer from the ketenes of the formulas (16) and (17) and 4.8 parts (0.035 mol) of a, a'-diamino m-xylene. 40.2 parts (100% of theory) of the crude reaction product of the formula are obtained

q and q 'as indicated in formula (18).

• Schmelzpunkt : 105-108 °C
• Elementaranalyse :
  

The crude product is recrystallized from dioxane for analysis purposes. The recrystallized product is in the form of a colorless powder. It is also free of unreacted ketene dimer.

• Melting point: 105-108 ° C
• Elemental analysis:
  

Example 14

The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 5.0 parts (0.025 mol) of 4,4'-diamino diphenyl ether. 30.3 parts (100% of theory) of the crude reaction product of the formula are obtained

q und q' wie in Formel (18) angegeben.

q and q 'as indicated in formula (18).

• Schmelzpunkt: 105-108 °C
• Elementaranalyse :
  

The crude product is recrystallized from acetone for analysis purposes. The recrystallized product is slightly yellowish. It is also free of unreacted ketene dimer.

• Melting point: 105-108 ° C
• Elemental analysis:
  

Example 15

The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 2.3 parts (0.025 mol) of 1,3-diamino-2 are used -propanol. 27.6 parts (100% of theory) of the crude reaction product of the formula are obtained

q und q' wie in Formel (18) angegeben.

q and q 'as indicated in formula (18).

• Schmelzpunkt : 98-100 °C.
• Elementaranalyse :
  

The crude product is recrystallized from dioxane for analysis purposes. The recrystallized product is in the form of a colorless powder. It is also free of unreacted ketene dimer.

• Melting point: 98-100 ° C.
• Elemental analysis:
  

Example 16

The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 1.8 parts (0.025 mol) of 1,2-diaminopropane are used. 27.1 parts (100% of theory) of the crude reaction product of the formula are obtained

q und q' wie in Formel (18) angegeben.

q and q 'as indicated in formula (18).

The crude product is recrystallized from ethyl acetate for analysis purposes. The recrystallized product is in the form of a colorless powder. It is also free of unreacted ketene dimer.

• Melting point: 98-100 ° C.
• Elemental analysis:
  

Example 17

q und q' wie in Formel (18) angegeben.The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 2.9 parts (0.025 mol) of 1,4-diaminocyclohexane are used. 28.2 parts (100% of theory) of the crude reaction product of the formula are obtained

q and q 'as indicated in formula (18).

• Schmelzpunkt: 120-125 °C
• Elementaranalyse :
  

The crude product is recrystallized from ethyl acetate for analysis purposes. The recrystallized product is in the form of a colorless powder. It is also free of unreacted ketene dimer.

• Melting point: 120-125 ° C
• Elemental analysis:
  

Application examples Examples 18 and 19

A fiber suspension made of bleached birch sulfate pulp and pine sulfate pulp in a weight ratio of 1: 1 in water of 10 ° dH (German degrees of hardness), which has a Schopper-Riegler degree of grinding of 35 ° and a solids content of 0.5%, is filled with 20% chalk and thereupon mixed with 0.01% PERCOL 292 ⁸ (cationic, high molecular weight (> 1,107) polyacrylamide) as an aid for retaining the finest cellulose fiber particles, the pH of the pulp suspension given in Table I below being established. The percentages relate to dry matter of auxiliaries and fillers, based on the solids content of the fiber suspension.

Formulations of the sizing agent are prepared by in each case 7% of the reaction products indicated as a crude product in powder form as a sizing agent, each with 3.5% POLYMIN P ^® (polyethyleneimine having a molecular weight from 10,000 to 100,000) as a retention agent in the presence of deionized water and glass beads having a diameter of 2 mm. The dispersions obtained are homogeneous, pourable and stable in storage. The percentages relate to the dry matter of sizing and retention agent, based on the total weight of the formulation.

Now the aqueous formulation of the sizing agent and the retention aid is added to the fibrous suspension in such a way that an amount of 0.5% dry matter of the sizing agent, based on the solids content of the fibrous suspension, is formed. The fiber suspension is then processed in a laboratory sheet former to paper sheets which, after a first drying at 130 ° C. for 3 minutes, have a basis weight of 80 g / m ² . The paper sheet thus obtained is subjected to an additional heat treatment at 140 ° C for 3 minutes.

Both surfaces of the paper sheets obtained, ie the surface obtained on the screen side of the sheet former and the opposite or top side, are checked for their sizing properties. For this purpose, the water absorption according to Cobb is measured after 30 seconds of exposure (WA Cobb ₃₀ ) according to DIN 53 132. The results of the WA Cobb ₃₀ measurements in g / m ^{2 of} the sieve side (SS) and top side (OS) before and after the heat treatment at 140 ° C and before and after storage for one day at 20 ° C are in the table below I specified. The lower the water absorption, the better the size of the paper. WA Cobb ₃₀ values over 100 correspond to a completely unsatisfactory sizing of the paper.

(See Table I page 17 f.) Examples 20 and 21

The procedure is as given in Examples 18 and 19, but in the formulations the reaction products given in Table II below are used as sizing agents.

The sizing results are summarized in Table II below.

(See Table II page 18 f.) Examples 22-24

The procedure is as described in Examples 18 and 19, but in the formulations the reaction products given in Table 111 below are used as sizing agents.

The sizing results are summarized in Table III below.

(See Table III page 20 f.) Examples 25 and 26

The procedure is as given in Examples 18 and 19, but in the formulations the reaction products given in Table IV below are used as sizing agents.

The sizing results are summarized in Table IV below.

(See Table IV page 21 f.) Example 27

The procedure is as described in Examples 18 and 19, but the reaction product set in Table V below is used as the sizing agent in the formulation.

The sizing results are summarized in Table V below.

(See table V page 22 f.) Examples 28 and 29

The procedure is as given in Examples 18 and 19, but in the formulations the reaction products given in Table VI below are used as sizing agents.

The sizing results are summarized in Table VI below.

Example 30

• 7 % Umsetzungsprodukt gemäss Beispiel 11 als Leimungsmittel
• 3,5 % POLYMIN P^* als Retentionsmittel
• 0,7 % Sorbitan-Monostearat als Oel-in-Wasser Emulgator
• 0,7% eines Adduktes aus Aethylenoxyd und Sorbitan-monostearat als Wasser-in-Oel Emulgator.
• Diese Formulierung ist homogen und lagerstabil.
• Die Leimungsergebnisse sind in der nachfolgenden Tabelle VII zusammengestellt.

The procedure is as described in Examples 18 and 19, but the following formulation of the sizing agent is used, which is emulsified in the presence of water in the molten state at 80 ° C.

• 7% reaction product according to Example 11 as a sizing agent
• 3.5% POLYMIN P ^* as a retention agent
• 0.7% sorbitan monostearate as an oil-in-water emulsifier
• 0.7% of an adduct of ethylene oxide and sorbitan monostearate as a water-in-oil emulsifier.
• This formulation is homogeneous and stable in storage.
• The sizing results are summarized in Table VII below.

(See Table VII page 23 f.)

Examples 31 and 34

The procedure is as described in Examples 18 and 19, but in the formulations the reaction products given in Table VIII below are used as sizing agents.

The sizing results are summarized in Table VIII below.

Claims (6)

1. A process for sizing paper or cardboard by adding, in any order or simultaneously, to an aqueous dispersion of the fibres, which dispersion may also contain fillers, at least

(A) one anionic hydrophobic sizing agent and

(B) one polymeric cationic retention aid,

in which process the sizing agent (A) is obtainable from

(a) ketene dimers whose hydrophobic substituents have at least 5 carbon atoms, said substituents containing only carbon and hydrogen, and

(b) diamines or oligoamines having 2 to 6 nitrogen atoms and 2 to 36 carbon atoms.

2. A process according to claim 1, wherein component (a) is a dimer of the ketenes of the formulae R₁―CH=C=0 and R₁―CH=C=0, in which R, and R₁' are identical or different and each is a hydrophobic substituent having at least 5 carbon atoms, provided that at least one of the radicals R, and R₁' has at least 8 carbon atoms.

3. A process according to either of claims 1 or 2, wherein component (b) is a diamine or oligoamine of the formula D₁―NH―A₁―NH₂, in which A₁ is alkylene, hydroxyalkylene, alkenylene or cycloalkylene having at most 12 carbon atoms, naphthylene or a radical of one of the formulae

D, is hydrogen or an alkyl or alkenyl radical which derives from fatty acids having 8 to 22 carbon atoms, E, and E₁' are each ethylene or n-propylene, n₁, n₂, n₃ and n₄ are each 1, 2 or 3, and m is an integer from 1 to 4.

4. An aqueous composition for carrying out the process according to any one of claims 1 to 3 by adding the sizing agent (A) and the retention aid (B) separately, in any order, to the dispersion of the fibres, which composition contains-the sizing agent (A), at least partly in the form of salts, and optionally also contains customary additives.

5. An aqueous composition for carrying out the process according to any one of claims 1 to 3 by adding the sizing agent (A) and the retention aid (B) simultaneously to the dispersion of the fibres, which composition contains

(A) 2 to 40 per cent by weight of sizing agent and

(B) 0.1 to 20 per cent by weight of retention aid,

each based on dry substance of (A) and (B) and on the weight of the aqueous composition, and optionally also contains customary additives.

6. Use of component (A) according to any one of claims 1 to 3 for sizing paper or cardboard.