EP0227600A1 - Process for sizing paper with anionic hydrophobic sizing agents and polymerized monoallylic amines as retention agents - Google Patents

Abstract

Conventional anionic hydrophobic sizing agents such as e.g. fatty acids, rosin size or a synthetic sizing agent that has at least one anionic group present in salt or acid form and at least one C5 - C22 alk(en)yl residue are particularly suitable for bulk sizing or surface sizing procedures for paper or cardboard when used in novel combination with a polymerised and possibly modified cross-linked monoallylamine as a retention aid.

Description

The present invention relates to a paper sizing process in which conventional anionic, hydrophobic sizing agents in a novel combination, together with polymerized monoallylamines as retention agents, produce good sizing effects both in the manufacture of paper from fiber suspensions (bulk sizing) and in the production of paper with a sized surface (surface sizing).

From e.g. European patent application 131 306 discloses polymerized monoallylamines which, however, are not used in paper manufacture as retention aids together with sizing agents, but rather as drainage accelerators and filter aids for fiber suspensions in the absence of sizing agents.

From e.g. European patent application 96 654 are anionic. hydrophobic. synthetic sizing agents are known which, however, are used together with e.g. Polyalkyleneimines or reaction products of epihalohydrins and polymerized diallylamines can be used as cationic retention agents.

It has now been found that the use of anionic, hydrophobic sizing agents together with polymerized monoallylamines or partially crosslinked with epichlorohydrin, polymerized monoallylamines as retention agents in a novel combination leads to particularly advantageous sizing effects in papermaking both in bulk and in surface sizing.

• (A) ein anionisches, hydrophobes Leimungsmittel und
• (B) ein Retentionsmittel, das ein polymerisiertes, gegebenenfalls modifiziertes, vernetztes Monoallylamin der Formel
  
  enthält, worin T. CI. Br. I, HS0₄, HS0₃, H₂P0₄, H₂P0₃, HCOO, CH₃COO oder C₂HsCOO. _Z1 eine Zahl von 10 bis 100 000 und z₂ eine Zahl von Null bis 100 000 bedeuten, einsetzt.

The present invention thus relates to a method for gluing paper or cardboard, which is characterized in that at least one

• (A) an anionic, hydrophobic sizing agent and
• (B) a retention aid which is a polymerized, optionally modified, crosslinked monoallylamine of the formula
  
  contains, where T. CI. Br. I, HS0 ₄ , HS0 ₃ , H ₂ P0 ₄ , H ₂ P0 ₃ , HCOO, CH ₃ COO or C ₂ HsCOO. _{Z1 is} a number from 10 to 100,000 and z _{2 is} a number from zero to 100,000.

In the process according to the invention, in the mass sizing of paper or cardboard, the components (A) and (B) are added to aqueous, cellulose-containing, optionally filler-containing fiber suspensions in any order or simultaneously, while in the case of surface sizing the paper is mixed with an aqueous liquor solution which contains the components ( A) and (B) contains, impregnated and dried.

• - die wässrigen Zusammensetzungen zur Durchführung des Papierleimungsverfahrens, die, sofern das Leimungsmittel (A) und das Retentionsmittel (B) bei der Massenleimung zur Faserstoffsuspension gleichzeitig gegeben werden oder als Leimflotte zur Oberflächenleimung des Papiers eingesetzt werden, sowohl das gegebenenfalls mindestens teilweise in Salzform vorliegende Leimungsmittel (A) als auch das Retentionsmittel (B) neben fakultativen, üblichen Zusätzen enthalten,
• - nach dem erfindungsgemässen Verfahren geleimtes Papier oder geleimter Karton und
• - die Verwendung der Kombination des Leimungsmittels (A) mit dem Retentionsmittel (B) der angegebenen Art zum Leimen von Papier oder Karton.

Further objects of the invention thus form

• - The aqueous compositions for carrying out the paper sizing process, which, if the sizing agent (A) and the retention agent (B) are added to the pulp suspension at the same time in the case of mass sizing, or are used as a glue liquor for surface sizing of the paper, both the sizing agent which is optionally present at least partially in salt form (A) as well as the retention agent (B) in addition to optional, conventional additives,
• - glued paper or glued cardboard according to the inventive method and
• - The use of the combination of the sizing agent (A) with the retention agent (B) of the specified type for sizing paper or cardboard.

If sizing agents of natural origin are used as component (A), fatty acids with at least 14 carbon atoms and resin glues, which are present as a crude product (rosin) or as a formulation (rosin size), are particularly suitable.

Fatty acids with 14 to 34, especially 16 to 28 and in particular 18 to 22 carbon atoms are preferred. Representatives of such fatty acids include myristin, myristole, lignocerin, cerotin, montan, myricine, melissin, especially palmitin, palmitolein and especially stearin, dioxystearin, arachine, behen, oil, Elaidin, linole, linolen, elaeostearin, gadolein. Cetaloin-erucic, ricinoleic and clupanodonic acid mentioned, with oleic, behenic and stearic acids being of particular interest. Easily accessible, technical mixtures of these fatty acids are also possible. In addition to fatty acids of natural origin, synthetic fatty acids, e.g. can be produced by oxosynthesis, are used as component (A).

The resin glue raw products are mainly rosin made from softwood stems (Root resin, wood rosin) or from cut bark of softwood (balsam resin, gum rosin) or around tall resin as a by-product in the production of sulfate cellulose (tall oil rosin). The resin acids contained in the resin glue raw product have as main components abietic acid or its derivatives such as neo-, dehydro-, dihydro-, tetrahydroabietic acid, levopimaric and palustric acid, or pimaric acid or its derivatives such as isopimaric acid. The ratio of abietic acid to pimaric acid depends on the origin of the raw product. Advantageously, the resin acids in the so-called reinforced resin glue (fortified rosin) are modified with an aliphatic, unsaturated dicarboxylic acid or its anhydride such as citraconic, mesaconic, itaconic, especially fumaric or maleic acid, especially maleic anhydride, by a Diels-Adler addition reaction. Formulated resin glues are, for example, resin soaps that are partially or completely saponified with, for example, sodium hydroxide or sodium carbonate and with partial saponification as paste (paste rosin size), with complete saponification with optional addition of paraffin wax as solid substance (dry rosin size) and with saponification to about 75 up to 90% with the addition of, for example, protective colloids as stabilizers as dispersion glue (free resin-containing emulsions, high free-rosin size emulsion). Such commercially available resin glues are described, for example, in TAPPI (Technical Association of the Pulp and Paper Industry) monograph No. 33 (1971).

Fatty acids and resin glue of the specified type have the advantage of their good accessibility and low procurement costs. However, higher amounts are necessary in order to achieve satisfactory sizing effects. In contrast, synthetic sizing agents produce satisfactory sizing effects with significantly lower amounts used and are therefore preferred over fatty acids and resin glue.

If synthetic sizing agents are used as component (A), those which have at least one anionic, salt-form or acidic group and at least one hydrophobic alkyl or alkenyl radical having 5 to 22 carbon atoms are particularly suitable.

Sizing agents known per se are preferred, the at least one acidic or salt-form hydroxyl, carboxyl or sulfo group, a single N, N-Cs-C ₂₂ dialkyl or dialkenylamide residue or a single Cs-C ₂₂ alkyl or alkenyl residue and a bridge member -O-CO-or -NH-CO-, whose -CO units are linked to the alkyl or alkenyl radical, or a bridge member -NH-CO-O-, -O-CO-NH- or - Have NH-CO-NH-.

worin A₁ und A₂ je eine anionische, d.h. in Salzform vorliegende oder acide, d.h. freie Carboxyl-, Hydroxyl-oder Sulfogruppe, D₁ durch Halogen, Nitro, Amino oder Hydroxyl substituiertes oder unsubstituiertes Phenylen, Naphthylen, Dihydronaphthylen oder Tetrahydronaphthylen, R₁ Alkyl oder Alkenyl mit 5 bis 22 Kohlenstoffatomen, Xi ein Brückenglied der Formel -O-CO-, -NH-CO-, -NH-CO-O-, -O-CO-NH-, -NH-CO-NH-, wobei endständige -CO-Einheiten des Brückengliedes an den Alkyl- oder Alkenylrest R₁ geknüpft sind, und m und n je 1 oder 2 bedeuten, vor allem der Formel

und

worin D₂ durch Chlor, Brom, Nitro, Amino oder Hydroxyl substituiertes oder unsubstituiertes Phenylen oder Naphthylen. R₂ Alkyl oder Alkenyl mit 5 bis 21 Kohlenstoffatomen, R₃ Alkyl oder Alkenyl mit 6 bis 22 Kohlenstoffatomen. X₂ -O- oder -NH- bedeuten und A₁ und n die angegebenen Bedeutungen haben, und insbesondere der Formel

worin Z₁ Chlor, Brom, Nitro oder Amino, R₄ Alkyl oder Alkenyl mit 15 bis 21 Kohlenstoffatomen und Ai die angegebenen Bedeutungen hat. der Formeln

und

worin Ai, R₄, X₂, m und n die angegebenen Bedeutungen haben und der Formeln

und

worin R₅ Alkyl oder Alkenyl mit 16 bis 22 Kohlenstoffatomen bedeutet und A₁, R₅, X₂, m und n die angegebenen Bedeutungen haben.Aromatic sizing agents of this type having a single alkyl or alkenyl radical correspond, for example, to the formula

wherein A ₁ and A ₂ each have an anionic, ie salt or acidic, ie free carboxyl, hydroxyl or sulfo group, D ₁ substituted by halogen, nitro, amino or hydroxyl or unsubstituted phenylene, naphthylene, dihydronaphthylene or tetrahydronaphthylene, R ₁ Alkyl or alkenyl having 5 to 22 carbon atoms, Xi is a bridge member of the formula -O-CO-, -NH-CO-, -NH-CO-O-, -O-CO-NH-, -NH-CO-NH-, terminal -CO units of the bridge member are linked to the alkyl or alkenyl radical R ₁ , and m and n each represent 1 or 2, especially of the formula

and

wherein D ₂ is substituted by chlorine, bromine, nitro, amino or hydroxyl or unsubstituted phenylene or naphthylene. R ₂ alkyl or alkenyl having 5 to 21 carbon atoms, R ₃ alkyl or alkenyl having 6 to 22 carbon atoms. X ₂ denotes -O- or -NH- and A ₁ and n have the meanings indicated, and in particular of the formula

wherein Z _{1 is} chlorine, bromine, nitro or amino, R _{4 is} alkyl or alkenyl having 15 to 21 carbon atoms and Ai has the meanings given. of the formulas

and

wherein Ai, R ₄ , X ₂ , m and n have the meanings given and the formulas

and

wherein R _{5 is} alkyl or alkenyl having 16 to 22 carbon atoms and A ₁ , R ₅ , X ₂ , m and n have the meanings given.

worin A₁, A₂ und A₃ je eine anionische, d.h. in Salzform vorliegende oder acide, d.h. freie Hydroxyl-, Carboxyl-oder Sulfogruppe, D₃ einen aromatischen oder cycloaliphatischen, zweiwertigen, gegebenenfalls durch Halogen substituierten Rest mit 5 bis 10 Kohlenstoffatomen oder gegebenenfalls verzweigtes Alkylen oder Alkenylen mit 2 bis 6 Kohlenstoffatomen. R₃ und R₃' je Alkyl oder Alkenyl mit 6 bis 22 Kohlenstoffatomen und n und m je 1 oder 2 bedeuten, vor allem der Formel

worin A₄ eine Sulfo- oder Carboxylgruppe, A₅ und A₆ je eine Hydroxyl- oder Carboxylgruppe, die in Salzform als anionische Gruppen oder als acide d.h. freie Gruppen vorliegen, D₄ Naphthylen, Phenylen, Di- oder Tetrahydrophenylen, Cyclohexylen, Norbornenylen, Hexachlornorbornenylen, C₂-C₄-Alkenylen oder C₂-C₆-Alkylen bedeuten und R₃, n und m die angegebenen Bedeutungen haben, und insbesondere der Formel

worin D_s einen zweiwertigen Rest der Formel

oder

R₅ Alkyl oder Alkenyl mit 16 bis 22 Kohlenstoffatomen und n 1 oder 2 bedeuten, wobei die Leimungsmittel der Formel (12) gegebenenfalls in Salzform vorliegen.Sizing agents containing a single dialkyl or dialkenylamide radical correspond, for example, to the formula

wherein A ₁ , A ₂ and A ₃ each have an anionic, ie salt or acidic, ie free hydroxyl, carboxyl or sulfo group, D ₃ an aromatic or cycloaliphatic, divalent, optionally substituted by halogen radical having 5 to 10 carbon atoms or optionally branched alkylene or alkenylene with 2 to 6 carbon atoms. R ₃ and R ₃ 'each represent alkyl or alkenyl having 6 to 22 carbon atoms and n and m each represent 1 or 2, especially of the formula

where A _{4 is} a sulfo or carboxyl group, A ₅ and A ₆ each have a hydroxyl or carboxyl group which are in salt form as anionic groups or as acidic, ie free, groups, D ₄ naphthylene, phenylene, di- or tetrahydrophenylene, cyclohexylene, norbornenylene, Hexachlornorbornenylen, C ₂ -C ₄ alkenylene or C ₂ -C ₆ alkylene mean and R ₃ , n and m have the meanings given, and in particular of the formula

wherein D _{s is} a divalent radical of the formula

or

R _{5 is} alkyl or alkenyl having 16 to 22 carbon atoms and n is 1 or 2, the sizing agents of the formula (12) optionally being in salt form.

worin D₆ geradkettiges oder verzweigtes Alkenylen mit 2 bis 6 Kohlenstoffatomen und 1 oder 2 Doppelbindungen oder Ethinylen, R₃ Alkyl oder Alkenyl mit 6 bis 22 Kohlenstoffatomen und X₂ -NH- oder -O-bedeuten, vor allem der Formel

worin D₇ geradkettiges oder verzweigtes Alkenylen mit 2 bis 4 Kohlenstoffatomen, R₅ Alkyl oder Alkenyl mit 16 bis 22 Kohlenstoffatomen bedeuten und X₂ die angegebenen Bedeutungen hat, und insbesondere der Formel

worin D₈ einen Alkenylenrest der Formel

oder

bedeutet und R₅ und X₂ die angegebenen Bedeutungen haben, wobei die Leimungsmittel der Formeln (13), (14) und (15) gegebenenfalls in Salzform vorliegen.Unsaturated aliphatic sizing agents with a single alkyl or alkenyl radical and a single carboxyl group correspond, for example, to the formula

wherein D ₆ straight-chain or branched alkenylene with 2 to 6 carbon atoms and 1 or 2 double bonds or ethynylene, R ₃ alkyl or alkenyl with 6 to 22 carbon atoms and X ₂ -NH- or -O-, especially the formula

wherein D _{7 is} straight-chain or branched alkenylene having 2 to 4 carbon atoms, R _{5 is} alkyl or alkenyl having 16 to 22 carbon atoms and X _{2 has} the meanings indicated, and in particular the formula

wherein D _{8 is} an alkenylene radical of the formula

or

and R ₅ and X _{2 have} the meanings given, the sizing agents of the formulas (13), (14) and (15) optionally being in salt form.

und

worin R₃ Alkyl oder Alkenyl mit 6 bis 22 Kohlenstoffatomen, X₃ -O-. -NH-oder -N(R₃')- und R₃' die für R₃ angegebenen Bedeutungen hat und R₃' und R₃ voneinander verschieden oder vorzugsweise gleich sind und insbesondere der Formeln

und

worin Rs Alkyl oder Alkenyl mit 16 bis 22 Kohlenstoffatomen und X₅ -O-, -NH- oder -N(R₅)- bedeuten, wobei die Leimungsmittel der Formeln (16), (17), (18) und (19) gegebenenfalls in Salzform vorliegen.Aromatic sizing agents with a single dialkyl or dialkenyl radical or alkyl or alkenyl radical and a single carboxyl group, which additionally have an anhydride group, correspond above all to the formulas

and

wherein R _{3 is} alkyl or alkenyl having 6 to 22 carbon atoms, X ₃ -O-. -NH-or -N (R ₃ ') - and R ₃ ' has the meanings given for R ₃ and R ₃ 'and R ₃ are different from one another or preferably identical and in particular of the formulas

and

wherein Rs is alkyl or alkenyl having 16 to 22 carbon atoms and X _{5 is} -O-, -NH- or -N (R ₅ ) -, the sizing agents of the formulas (16), (17), (18) and (19) optionally in salt form.

Compared to the sizing agents of the type specified above, which have a single hydrophobic alkyl, alkenyl, dialkylamide or dialkenylamide residue, sizing agents with at least two hydrophobic alkyl or alkenyl residues are preferred. Such preferred sizing agents have at least one acidic or salted phosphate, carboxyl or sulfo group or at least one anionic dicarbonylmethylene group -CO-CH ₂ -CO-, dicarbonylmethylene group -CO- CH-CO-, sulfonylcarbonylimide group -S0 ₂ -NH-CO- or disulfonylimide group -SO ₂ -NH-SO ₂ -, at least two C ₅ -C ₂₂ alkyl or alkenyl radicals, where at least one of these radicals has at least 8 carbon atoms, and at least one bridge member connecting adjacent alkyl or alkenyl radicals with at least 1 carbon atom and 2 heteroatoms in the main chain.

Sizing agents with 1 or 2 anionic sulfonylcarbonylimide groups, 2 to 6 C ₅ -C ₂₂ alkyl or alkenyl radicals, at least one of which has at least 8 carbon atoms and a bridge member of the formula (20) -CO-NH-D connecting adjacent alkyl or alkenyl radicals ₉ - (SO ₂ -NH-CO) _m -, in which D _{9 is} a divalent or trivalent, aliphatic, cycloaliphatic or aromatic radical having at most 10 carbon atoms and m is 1 or 2, are described, for example, in European patent application 144 284.

worin Q₁, Qz und Q₃ je -O-R₆, -NH-R₆,

oder

R₆ und R₇ Alkyl oder Alkenyl mit vorzugsweise 8 bis 22, insbesondere 16 bis 20 Kohlenstoffatomen und E₁ und E2 je Propylen oder vorzugsweise Ethylen, p eine ganze Zahl von 1 bis 5, vorzugsweise 1, 2 oder 3, insbesondere 2, q eine ganze Zahl von 1 bis 9 und D₉ und m die angegebenen Bedeutungen haben, vor allem der Formel

oder

worin D₉, E₁, E2, Rs, R₇, m, p und q die angegebenen Bedeutungen haben, und insbesondere der Formel

oder

worin D₁₀ Cycloalkylen, Naphthylen, vor allem durch Methyl substituiertes Phenylen, vorzugsweise Toluylen und Xylylen, ins besondere unsubstituiertes Phenylen oder C₂-C₆-Alkylen bedeutet und R₆, p und q die angegebenen Bedeutungen haben.Such sizing agents generally correspond to the formula

where Q ₁ , Qz and Q ₃ each -OR ₆ , -NH-R ₆ ,

or

R ₆ and R _{7 are} alkyl or alkenyl with preferably 8 to 22, in particular 16 to 20 carbon atoms and E ₁ and E2 per propylene or preferably ethylene, p is an integer from 1 to 5, preferably 1, 2 or 3, in particular 2, q an integer from 1 to 9 and D ₉ and m have the meanings given, especially the formula

or

wherein D ₉ , E ₁ , E2, Rs, R ₇ , m, p and q have the meanings given, and in particular of the formula

or

in which D ₁₀ denotes cycloalkylene, naphthylene, especially phenylene substituted by methyl, preferably toluylene and xylylene, in particular unsubstituted phenylene or C ₂ -C ₆ alkylene and R ₆ , p and q have the meanings given.

Sizing agents with 1 to 6 anionic sulfonylcarbonylamide or disulfonylamide group and 2 to 6 C ₅ -C ₂₂ alkyl or alkenyl radicals, at least one of which has at least 8 carbon atoms, and 1 to 5 bridging members which connect two of these alkyl or alkenyl radicals, where each bridge member has 1 to 10 carbon atoms, 1 to 5 nitrogen atoms, 1 or 2 sulfur atoms and optionally 1 or 2 oxygen atoms in the main chain, are described, for example, in European patent application 123 763.

oder

worin E_i und E2 je Propylen oder vor allem Ethylen E3 unsubstituiertes oder durch Halogen, Ci-C₄-Alkyl oder -Alkoxy substituiertes Phenyl, Q₄ -O-. -NH- oder -N. Q₅ -NH- oder -N . R₆ R'₆ und R₇ je Alkyl oder Alkenyl mit vorzugsweise 8 bis 22, insbesondere 16 bis 20 Kohlenstoffatomen, R₈ und R₉ je die für R₆ und R₇ angegebenen Bedeutungen haben oder je unsubstituiertes oder durch Methyl substituiertes Phenyl, vorzugsweise Xylyl, insbesondere Tolyl, m, n, s und t je 1 oder 2. p eine ganze Zahl von 1 bis 5, vorzugsweise 1, 2 oder 3. insbesondere 2, bedeuten, wobei s und t 2 sind, sofern Q₄ und Q₅ für -N stehen. vor allem der Formel

oder

worin n, m, u und v je 1 oder 2 und Z₂ und Z₃ je Halogen, vorzugsweise Brom, insbesondere Chlor, oder vor allem C₁-C₄-Alkyl- oder-Alkoxy, vorzugsweise Methyl, insbesondere Methoxy bedeuten und E₁, R₅, R₇, R₈, p und t die angegebenen Bedeutungen haben, und insbesondere der Formel

oder

worin E₁, R₆, R₇, R₈, Z₂ und m die angegebenen Bedeutungen haben.Such sizing agents generally correspond to the formula

or

wherein E _i and E2 each propylene or especially ethylene E3 phenyl unsubstituted or substituted by halogen, Ci-C ₄ alkyl or alkoxy, Q ₄ -O-. -NH- or -N. Q ₅ -NH- or -N. R ₆ R ' ₆ and R ₇ each alkyl or alkenyl with preferably 8 to 22, in particular 16 to 20 carbon atoms, R ₈ and R ₉ each for R ₆ and R ₇ have the meanings indicated or each unsubstituted or methyl-substituted phenyl, preferably xylyl, in particular tolyl, m, n, s and t each 1 or 2. p is an integer from 1 to 5, preferably 1, 2 or 3. in particular 2 , where s and t are 2 if Q ₄ and Q _{5 are} -N. especially the formula

or

wherein n, m, u and v each represent 1 or 2 and Z ₂ and Z ₃ each halogen, preferably bromine, especially chlorine, or especially C ₁ -C ₄ alkyl- or alkoxy, preferably methyl, especially methoxy and E ₁ , R ₅ , R ₇ , R ₈ , p and t have the meanings given, and in particular the formula

or

wherein E ₁ , R ₆ , R ₇ , R ₈ , Z ₂ and m have the meanings given.

oder

wobei Formel (42) zutrifft, sofern Diamine als Ausgangskomponente und formel (43) zutrifft, sofern Oligoamine als Ausgangskomponente eingesetzt werden, und in Formeln (42) und (43) G Alkylen, Hydroxyalkylen. Alkenylen oder Cycloalkylen mit höchstens 12 Kohlenstoffatomen, Naphthylen, einen Alkaryl-oder Arylrest der Formel

oder

oder einen heterocyclischen Rest der Formel

E₁ und E2 je Propylen oder vorzugsweise Aethylen, R₉ Wasserstoff oder einen sich von Fettsäuren mit 8 bis 12 Kohlenstoffatomen ableitenden Alkyl- oder Alkenylrest und R₆ und R₇ Alkyl oder Alkenyl mit vorzugsweise 8 bis 22, insbesondere 16 bis 20 Kohlenstoffatomen, i₁, i₂, i₃ und i₄ je 1, 2 oder 3 und y eine ganze Zahl von 1 bis 4 bedeuten.Sizing agents with 2 to 6 dicarbonylmethylene groups, 4 to 12 C ₅ -C ₁₂ alkyl or alkenyl residues, at least one of which has at least 8 carbon atoms, and 1 to 5 bridging members which connect two of these alkyl or alkenyl residues, each bridging member having 4 to Has 16 carbon atoms and 2 nitrogen atoms in the main chain, are described for example in European patent application 105 028. Such sizing agents are obtainable from hydrophobic ketene dimers and di- or oligoamines and generally correspond to the formula

or

where formula (42) applies if diamines are the starting component and formula (43) applies if oligoamines are used as the starting component, and in formulas (42) and (43) G alkylene, hydroxyalkylene. Alkenylene or cycloalkylene with at most 12 carbon atoms, naphthylene, an alkaryl or aryl radical of the formula

or

or a heterocyclic radical of the formula

E ₁ and E2 each propylene or preferably ethylene, R ₉ hydrogen or an alkyl or alkenyl radical derived from fatty acids having 8 to 12 carbon atoms and R ₆ and R ₇ alkyl or alkenyl preferably having 8 to 22, in particular 16 to 20 carbon atoms, i ₁ , i ₂ , i ₃ and i ₄ each 1, 2 or 3 and y is an integer from 1 to 4.

Sizing agents with 1 or 2 phosphate, carboxyl, sulfo, dicarbonylethylene or dicarbonylmethylene groups, 2 to 4 C ₅ -C ₂₂ alkyl or alkenyl radicals, at least one of which has at least 8 carbon atoms, and 1 or 2 these alkyl or Bridge members connecting alkenyl radicals, each bridge member having 1 to 12 carbon atoms and, as heteroatoms in the main chain, 2 or 3 oxygen atoms, 2 to 4 nitrogen atoms, 1 or 2 oxygen atoms and 1 nitrogen atom or 2 nitrogen and 2 oxygen atoms, are described, for example, in European Patent Application 96 654.

oder

I=CHE> >worin R₆ und R₇ je Alkyl oder Alkenyl mit vorzugsweise 8 bis 22, insbesondere 16 bis 20 Kohlenstoffatomen und Y₁ eine acide oder in Salzform vorliegende Gruppe -P(O)(OH)₂, -SO₃H, -CO-CH=CH=COOH oder -CO-CH₂-CH₂-COOH und m 1 oder 2 bedeuten.Such sizing agents preferably have 1 or 2 phosphate, carboxyl or sulfo groups, 2 to 4 C ₅ -C ₂₂ alkyl or alkenyl radicals and 1 or 2 bridging elements with 2 to 12 carbon atoms and either 2 oxygen atoms or connecting adjacent alkyl or alkenyl radicals 4 nitrogen atoms, or 1 or 2 oxygen atoms and 1 nitrogen atom, or 2 oxygen and 2 nitrogen atoms in the main chain and generally correspond to the formula

or

I = CHE>> wherein R ₆ and R _{7 are} each alkyl or alkenyl with preferably 8 to 22, in particular 16 to 20 carbon atoms and Y _{1 is} an acidic or salt group -P (O) (OH) ₂ , -SO ₃ H , -CO-CH = CH = COOH or -CO-CH ₂ -CH ₂ -COOH and m is 1 or 2.

oder

entsprechen, worin Y₂ eine acide oder in Salform vorliegende Gruppe der Formel (58) -(CH₂)₃-SO₃H, (59) -CH₂-COOH, (60) -CO-L-COOH. Y₃ eine acide oder in Salzform vorliegende Gruppe der Formel

L Ethylen, Propylen, Ethenylen, 1,2-Dimethylethenylen, Methylethenylen, Prop-1-en-1,2-ylen, Cyclohexylen, Biscyclo-(2,2,1)-hept-2-enylen, Phenylen oder Carboxyphenylen, R₆ und R₇ je Alkyl oder Alkenyl mit vorzugsweise 8 bis 22, insbesondere 16 bis 20 Kohlenstoffatomen, und n, m und u je 1 oder 2 bedeuten.In a further embodiment, the sizing agents described in European patent application 96 654 have a sulfo group or one or two carboxyl groups, two C _S -C ₂₂ alkyl or alkenyl radicals, a bridge member with 4 having 8 carbon atoms and 2 connecting the two alkyl or alkenyl radicals or 3 nitrogen atoms in the main chain, which are generally of the formula

or

correspond in which Y _{2 is} an acidic or salified group of the formula (58) - (CH ₂ ) ₃ -SO ₃ H, (59) -CH ₂ -COOH, (60) -CO-L-COOH. Y _{3 is} an acidic or salt group of the formula

L ethylene, propylene, ethenylene, 1,2-dimethylethenylene, methylethenylene, prop-1-en-1,2-ylene, cyclohexylene, biscyclo- (2,2,1) -hept-2-enylene, phenylene or carboxyphenylene, R ₆ and R ₇ each represent alkyl or alkenyl with preferably 8 to 22, in particular 16 to 20 carbon atoms, and n, m and u each represent 1 or 2.

oder

entsprechen, worin R₆ Alkyl oder Alkenyl mit vorzugsweise 8 bis 22, insbesondere 16 bis 20 Kohlenstoffatomen und m 1 oder 2 bedeuten.The European patent application 96 654 also discloses sizing agents, which in a further embodiment, one or two anionic Dicarbonylmethylen- or Dicarbonylmethingruppen, two or three Cs-C ₂₂ alkyl or alkenyl radicals and these alkyl or alkenyl groups connecting bridge member having 3 to 12 carbon atoms and have 2 or 3 oxygen atoms or 4 nitrogen atoms in the main chain and generally of the formula

or

correspond in which R _{6 is} alkyl or alkenyl with preferably 8 to 22, in particular 16 to 20 carbon atoms and m is 1 or 2.

oder

entsprechen, worin R₆ und R₇ je Alkyl oder Alkenyl mit vorzugsweise 8 bis 22, insbesondere 16 bis 20 Kohlenstoffatomen und m, n und u je 1 oder 2 bedeuten.European patent application 96 654 also describes sizing agents of another preferred embodiment which also have one or two carboxyl groups which may be in salt form, 2 to 4 C ₅ -C ₂₂ alkyl or alkenyl radicals and a bridge member connecting these alkyl or alkenyl radicals Have 4 to 6 carbon atoms and either 2 or 3 oxygen atoms or 2 nitrogen atoms, or 1 nitrogen atom and 1 or 2 oxygen atoms, which are generally of the formula

or

correspond in which R ₆ and R _{7 are} each alkyl or alkenyl preferably having 8 to 22, in particular 16 to 20 carbon atoms and m, n and u each being 1 or 2.

Sizing agents which are of primary interest and are also disclosed in European patent application 96 654 have an acidic or salted phosphate, carboxy or sulfo group, two or three Ca-C22-alkyl or alkenyl residues and a bridge member with 2 to 6 carbon atoms and either 2 oxygen atoms or 2 nitrogen atoms or one oxygen atom and one nitrogen atom in the main chain.

oder

worin R₆ und R₇ je Alkyl oder Alkenyl mit vorzugsweise 8 bis 22, insbesondere 16 bis 20 Kohlenstoffatomen und Y₄ eine acide oder in Salzform vorliegende Phosphat-, Carboxyl- oder insbesondere Sulfogruppe bedeuten.Such sizing agents generally correspond to the formula

or

wherein R ₆ and R ₇ each represent alkyl or alkenyl with preferably 8 to 22, in particular 16 to 20 carbon atoms and Y _{4 is} an acidic or salt-form phosphate, carboxyl or in particular sulfo group.

worin _Z1 eine Zahl von 10 bis 100 000 ist.The retention agent used as component (B) contains the poly (monoallylamine) of the formula (1) disclosed, for example, in European patent application 131 306. If the poly (monoallylamine) is obtained in the presence of at most 1 mol% triallylamine according to European patent application 131 306, the retention aid used according to the invention contains a polymerized, modified, slightly crosslinked monoallylamine. If the poly (monoallylamine) is also obtained in accordance with European patent application 131 306 in the presence of at most 0.5 percent by weight epichlorohydrin, the retention agent contains a polymerized, slightly crosslinked monoallylamine. However, the retention aid preferably consists of the unmodified and uncrosslinked, polymerized monoallylamine of the formula (1) which is obtained by polymerizing the corresponding monoallylamine salt in a polar solvent in the absence of triallylamine and epichlorohydrin. A polymerization initiator is required to produce the polymerized monoallylamine from the monoallylamine salt. which has an azo group and cationic nitrogen atoms and is described, for example, in US Pat. No. 4,504,640. In formula (1), z ₂ stands for zero, provided that after the polymerization of the monoallylamine salt has ended, the acid HT is completely removed, for example by neutralization with a strong base such as sodium hydroxide or by a strongly basic ion exchanger. If the acid HX is not removed, the retention agent is cationic and consists of the polymerized monoallylamine of the formula (1). where z _{2 stands} for 10 to 100,000. The cationic retention agent of primary interest consists of a polymerized monoallylamine of the formula

where _{Z1 is} a number from 10 to 100,000.

According to the process, in the case of the mass sizing of paper or cardboard, 0.02 to 6 percent by weight of the sizing agent (A) and 0.02 to 3 percent by weight of the renting agent (B) and generally 0.02 when using synthetic sizing agents of the type specified as component (A) to 3. preferably 0.05 to 3. in particular 0.1 to 0.8 percent by weight of the sizing agent (A) and 0.02 to

3. preferably 0.05 to 3. in particular 0.1 to 0.4 percent by weight of the retention agent (B). based on the dry matter of (A) and (B) and on the solids content of the fiber suspension used. 0.02 to about 0.05 percent by weight of the sizing agent (A) and the retention agent (B) are only sufficient for the so-called "size press control", which cannot be determined using conventional sizing tests (see, for example, the article "Control and Understanding of Size Press Pickup" by DR Dill in the journal "Proceedings of the TAPPI" Volume 57, No. 1 of January 1974, pages 97-100.

When using a fatty acid or resin size as component (A) in the mass sizing, however, at least 0.2% by weight, preferably 0.3 to 6, in particular 0.5 to 4% by weight of the sizing agent (A) and at least 0.1% by weight, preferably 0.1 to 2, in particular 0.15 to 1 percent by weight of the retention agent (B), based in each case on dry matter at (A) and (B) and on the solids content of the fiber suspension, are used.

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 of about 10 ° to about 60 °, especially 20 to 60 °, preferably 20 to 45 °, in particular 25 to 35 °. It usually contains cellulose, especially softwood, e.g. Pinewood, or hardwood, i.e. Hardwood, e.g. Beech wood, which, e.g. the sulfite or especially the sulfate process is produced. 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 for example article "Developmetns in Refiner Mechanical Pulping" by SA Collicutt and co-workers in "Proceedings of the TAPPI", Volume 64, No. 6 June 1981, pages 57 to 61) can be considered.

The fiber suspension can also contain organic or mineral fillers. Organic fillers include synthetic pigments, e.g. Polycondensation products made from urea or melamine and formaldehyde with large specific surfaces, which are in highly dispersed form and e.g. in British patents 1,043,937 and 1,318,244 are described as mineral fillers, among others. Montmorillonite, titanium dioxide, calcium sulfate and especially talc, colin 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 optional fillers of the type specified.

The pH of the pulp suspension can be in a wide range, e.g. Values from about 3.5 to about 10 can be present.

When adding e.g. 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 about 3.5 to about 7, preferably 5 to 7, especially 5 to 6, can be added in the absence of calcium carbonate by adding acids, e.g. Sulfuric or formic acid or especially from e.g. latent acidic sulfates, e.g. Aluminum sulfate (alum) can be obtained.

Preference is given to fiber suspensions which, if appropriate by adding chalk, have a pH of about> to about 9 and are advantageous in this respect. that possible signs of corrosion on the sensitive paper machines are excluded. In addition, the shelf life of paper or cardboard which has been sized at pH values of 7 to 9 of the fiber suspension is clearly superior to those which have been sized at pH values of 3.5 to <7.

The fibrous suspension can also contain additives such as e.g. Starch or its degradation products that increase fiber / fiber or fiber / filler bonding.

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

The pulp suspension is further processed in the mass sizing process according to the invention in a manner known per se on sheet formers or preferably continuously on paper machines of the usual type to 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, for example, 50 to 200 g / m ² are obtained.

For surface sizing of the paper in the process according to the invention, the glue liquor, which contains components (A) and (B), is applied to the paper, for example by spraying on, preferably by padding, generally at room temperature (15-25 ° C.). The impregnated paper is then dried at 60 to 140 ° C., preferably 90 to 110 ° C. for 0.1 to 10, preferably 2 to 6 minutes. After drying, a paper is obtained which has a surface application of sizing and retention agent 50 to 200, preferably 60 to 150, in particular 60 to 120 mg / m ² .

The paper to be sized according to the invention is any type of paper with any basis weight, e.g. paper and cardboard made from bleached and unbleached sulfite or sulfate cellulose. 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, only the sizing agent (A), provided that the sizing agent and the retention agent (B) are added separately to the fiber suspension in the course of the mass sizing. In this case, the preparation generally contains the sizing agent in whole or in part in the form of its salts (obtained using, for example, ammonia, an alkyl or alkanolamine or an alkali metal hydroxide of the type specified in the ratios given above). In general, such compositions contain 5 to 30, preferably 5 to 20 percent by weight of dry substance of the sizing agent, which is at least partially in salt form, based on the total weight of the aqueous composition.

On the other hand, in addition to the optional optional additives, provided that the sizing agent (A) and the retention agent (B) are added to the fiber suspension at the same time as the mass sizing, (A) contains 2 to 40, preferably 5 to 30, in particular 5 to 10 percent by weight Sizing agent (calculated as dry matter), based on the total weight of the aqueous composition, the sizing agent possibly being in salt form, and (B) 0.1 to 20, preferably 0.5 to 10, in particular 3 to 8 percent by weight retention agent (calculated as dry matter ), based on the total weight of the aqueous composition.

The aqueous compositions of the type indicated optionally contain surface-active compounds, e.g. Dispersants or further emulsifiers and / or water-soluble organic solvents. As dispersants and emulsifiers are e.g. Conventional lignin sulfonates, lignin carboxylates, carboxymethyl cellulose, ethylene oxide adducts of alkylphenols, fatty amines, fatty alcohols or fatty acids, fatty acid esters of polyhydric alcohols, substituted benzimidazoles or condensation products from formaldehyde and aromatic sulfonic acids, especially naphthalenesulfonic acids. Other surface-active compounds are preferably anionic surfactants, especially sulfate surfactants, e.g. Diethanolamine lauryl sulfate, sodium lauryl sulfate or ethoxylated lauryl sulfates. Possible water-soluble, organic solvents include aliphatic ethers having 1 to 10 carbon atoms, e.g. Dioxane, ethylene glycol n-butyl ether or diethylene glycol monobutyl ether or alcohols with 1 to 4 carbon atoms, e.g. Isopropanol, ethanol or methanol.

If the aqueous compositions contain additives of the type specified, the weight ratio (component (A)): (additives) is 1: 0.02 to 1: 0.3, preferably 1: 0.05 to 1: 0.1, based on dry substance sizing agents and additives.

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) usually partly 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) at at most 90 ° C., preferably about 50 to 85 ° C. for emulsions, in particular about 15 up to about 25 ° C. in the case of dispersions, resulting in storage-stable, homogeneous, further dilutable emulsions or preferably dispersions, since the sizing agents, together with the retention aids or the sizing agents which are present entirely or at least partially as salts, are generally self-dispersing or self-dispersing on their own. are emulsifying, the use of dispersants or Em ulgators generally not required. 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. For the surface sizing of paper, the glue liquor required for this is prepared by diluting with water the emulsions or dispersions specified above which contain both the sizing agent (A) and the retention agent (B). The emulsions or dispersions are diluted so that a glue liquor is formed which (A) 0.02 to 0.4, preferably 0.05 to 3, in particular 0.05 to 1 percent by weight of sizing agent (calculated as dry matter), based on the total weight the aqueous glue liquor, the sizing agent optionally being in salt form, and (B) 0.01 to 0.2, preferably 0.05 to 0.1, in particular 0.3 to 0.8 percent by weight retention agent (calculated as dry substance). based on the total weight of the aqueous glue liquor.

As an advantage of the method according to the invention, it should be mentioned that in the bulk sizing using synthetic sizing agents, fiber suspensions of the most varied types with relatively particularly small amounts of sizing and retention aids can be processed in a simple manner to paper, which has good sizing properties (alkali drop test, ink floating time and especially water absorption according to Cobb). This also applies to surface sizing, in which the good sizing effects can be achieved even with small area applications of sizing and retention agents. In particular, the small area orders enable a quick working process, so that at Drying temperature of, for example, 90 to 110 C, good surface sizes can be achieved within approximately 20 to 40 seconds. When using fatty acids or resin glue as well as synthetic sizing agents, the paper sized according to the process has good mechanical properties. ie. good strengths, especially good tensile strength. Good reproducibility of the process is guaranteed for both mass and surface sizing. In particular, pulp suspensions containing wood pulp or waste paper can be processed for mass sizing. The compatibility of the combination of sizing agents and retention agents used according to the invention with different fillers such as kaolin and also various additives. such as alum in the acidic area of the fiber suspensions in bulk sizing is advantageous. The combination of sizing and retention agents used according to the invention has good compatibility with the customary auxiliaries such as dyes used in the paper industry. Pigments. Binders. especially optical brighteners and other additives. Above all, the combination of sizing and retention agents used does not tend to form undesirable foams. Compared to other, conventional retention aids, the use of the retention agent of the specified type in the combination of sizing and retention agents used leads to significantly reduced foaming. In addition, the degree of whiteness of the sized paper is not significantly influenced by the sizing and can even be improved in both the mass and the surface sizing. Furthermore, the generally high storage stability of the dispersions of synthetic sizing agents of the type indicated is of great advantage.

The parts and percentages given in the following manufacturing instructions and working examples relate to the weight.

Manufacturing regulations for sizes Regulation A: step 1

270.5 parts of stearyl alcohol (1 mol) and 49 parts of maleic anhydride (0.5 mol) are melted at 70 ° C. 1 part of sodium bisulfate is added to this melt as a catalyst. The reaction mixture is heated to 150 ° C. and at for 7 hours at this temperature while stirring, the water formed by the reaction being removed from the reaction mixture After cooling the reaction mixture to 70 ° C., 302.4 parts of molten distearate of maleic acid (98% of theory) are obtained.

Level 11

Schmelzpunkt: 170-172°C.621 parts of molten maleic acid distearyl ester obtained in stage I (1 mol), 218.6 parts of sodium pyrosulfite 100% (1.15 mol) and 150 parts of water are heated to the reflux temperature of about 98 ° C. and for 20 hours at this temperature with stirring held. The reaction mixture is cooled to 30 ° C. and added to 8400 parts of water. The resulting fine suspension is kept under stirring for 1 hour at room temperature (15 to 25 ° C). The suspension is filtered off and the crude product is washed with water until the wash water is sulfite-free. After drying at 80 ° C. under reduced pressure, 717 parts (99% of theory) of the compound of the formula are obtained

Melting point: 170-172 ° C.

Regulation B:

Schmelzpunkt: 62-66°C.27.5 parts of pyrocatechol (0.25 mol) and 8.7 parts of pyridine (0.11 mol) are dissolved in 100 parts of tetrahydrofuran at 50 ° C. A solution of 30.3 parts of stearic acid chloride (0.1 mol) in 50 parts of tetrahydrofuran is added to this solution at 50 ° C. within 30 minutes. The reaction mixture is heated to the reflux temperature of about 67 ° C., kept at this temperature for 4 hours with stirring and then cooled to 25 ° C. 250 parts of an aqueous 0.5 N hydrochloric acid solution are added to the reaction mixture, the product precipitating. The product is filtered off, washed with 500 parts of water at 60 ° C. and dried under reduced pressure at 60 ° C. 36.4 parts of the compound of the formula are obtained as white powder

Melting point: 62-66 ° C.

Regulation C:

Schmelzpunkt: 75-77°C.54.6 parts of o-aminophenol (0.5 mol) are heated to 50 ° C. in 200 parts of pyridine. 151 parts of stearic acid chloride (0.5 mol) are added to this solution in the course of 1 hour, the stearic acid chloride being used as a melt at 40 ° C. The temperature of the reaction mixture increases automatically to 65 ° C., a suspension being formed which is kept under stirring for 4 hours at 50 ° C. The reaction mixture is then further heated to 90 ° C. and added to 4000 parts of deionized water with vigorous stirring. The dark brown colored suspension is filtered off and the product is washed with 300 parts of water and dried at 40 ° C. under reduced pressure. 182 parts of the compound of the formula are obtained as a light beige powder

Melting point: 75-77 ° C.

Manufacturing instructions for a retention aid Regulation D:

The procedure is analogous to that of Example 1 of European Patent Application 131 306, but the 2,2'-azobis (2-ami - dinopropane) hydrochloride.

step 1 Monoallyl hydrochloride

570 parts (10 mol) of monoallylamine are added to a 35% strength aqueous hydrochloric acid solution at 5 to 10 ° C. with cooling. The colorless, clear solution is then dried at 20 torr and 60 ° C. in a rotary evaporator. To remove the water of crystallization, the crude product is mixed with toluene several times and dried again in a rotary evaporator. The crystals of monoallyl hydrochloride obtained are dried at 160 torr and 80 'C.

Stage II Poly (monoallyl hydrochloride

To a solution of 59.0 parts (0.63 mol) of the dried monoallyl hydrochloride in 21 parts of water, 0.4 part (0.0015 mol) of 2,2'-azobis (2-amidinopropane) hydrochloride, dissolved in 3 parts of water, given. The yellowish reaction solution is polymerized with stirring in an inert nitrogen atmosphere at 50 ° C. for 11 hours. The reaction mixture is then mixed again with 0.4 part of the polymerization initiator mentioned in 3 parts of water and polymerized for a further 5 hours with stirring. The reaction mixture is then kept at 50 ° C. for a further 50 hours without stirring. For working up, the reaction mixture is added to 800 parts of methanol. The precipitate which has precipitated as a viscous, sticky mass is filtered off and extracted with methanol in Soxhlet for 22 hours. The sleeve residue is then dried at 50 C and 160 Torr. 49 parts of poly (monoallyl hydrochloride) are obtained.

Application examples

Example 1: a fiber suspension 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 freeness of 35 and a solids content of 0.50%, with 20% chalk as Filler and then with 0.01% PERCOL® 292 (cationic. High molecular weight (MW> 1 • 10 ⁷ ) polyacrylamide) as auxiliary to Retain the finest cellulose fiber particles, resulting in a pH value of 7.8 for the pulp suspension. The percentages relate to dry matter of auxiliaries and fillers. based on the solids content of the fiber suspension.

A formulation of the combination of the sizing agent and the retention aid is prepared by deionizing 25 parts of the sizing agent according to regulation A as a solid, as is obtained in the production, 1.25 parts of a condensation product of a naphthalenesulfonic acid and formaldehyde as a dispersant and 73.75 parts Water in the presence of glass beads with a diameter of 2 mm at room temperature (15 to 25 C) stirred to 100 parts of a dispersion of the sizing agent. The dispersion obtained is pourable, homogeneous and stable in storage. This dispersion is mixed with 250 parts of a 10%. mixed aqueous solution of the retention aid according to regulation D. The dispersion is then diluted with deionized water. that a formulation is created that is 1% sizing agent and 1% retention aid. based on the dry substance of sizing and retention agent and on the total weight of the formulation. contains.

Now the aqueous formulation of the sizing agent and the retention aid is added to the fiber suspension in such a way that an amount of 0.15% each of dry substance of the sizing agent according to regulation A and of the retention agent according to regulation D, based on the solids content of the fiber suspension. arises. The fibrous suspension is then processed in a Rapid-Köthen sheet-forming device (see Zellcheming leaflet V / 8/76, Darmstadt, Association of Pulp and Paper Chemists and Engineers) into sheets of paper, which after drying in an ironing press are absent of steam at 130 ° C for 3 minutes have a basis weight of 80 g / m ² .

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 tested for their sizing properties. For this purpose, the water absorption according to Cobb is measured after 30 seconds exposure (WA Cobb ₃ α) according to DIN 53 132. The results of the measurements in WA Cobb ₃ g / m ² on the wire side (SS) and upper side (OS) after drying at 130 ° C and after storage for two weeks at 23 ° C and 50 _^0/0 relative humidity are given in Table I below. 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.

Similar results are also achieved if, instead of 25 parts of the sizing agent according to regulation A, 25 parts of the sizing agent according to regulation B or 25 parts of the sizing agent according to regulation C are used.

Example 2: One proceeds as in 3 Eispie! 1, but gives the retention agent separately to the fiber suspension. For this purpose, 25 parts of the sizing agent according to regulation A as a solid, 1.25 parts of the stated dispersant and an aqueous, 1% sodium hydroxide solution in the presence of deionized water and glass beads are stirred at room temperature so that 100 parts of a dispersion are formed has a pH of 7.0. The dispersion obtained is pourable, homogeneous and stable in storage. A 100% aqueous solution of the retention agent according to regulation D is added to the fibrous suspension first and 10 seconds afterwards the 250% dispersion of the sizing agent obtained is added in such a way that an amount of 0.2% of the dry matter of the sizing and retention agent is used, based on the solids content of the fiber suspension. After processing the fiber suspension into paper as specified in Example 1, the sizing results given in Table 11 below are achieved:

Example 3: The procedure described in Example 1 is followed, however, unused waste (waste paper from a printing house) containing 35% bleached wood fibers is used as the fiber suspension. The fiber suspension has a Schopper-Riegler freeness of 34 ° and a solids content of 3.94%. The fibrous suspension is mixed with 5% kaolin as a filler and 4% alum as an additive, based on the dry matter of the filler and the additive and on the solids content of the fibrous suspension. The pH of the fiber suspension is then adjusted to 5.5 by adding an aqueous 1N sulfuric acid solution. The formulation according to Example 1, which contains 1% sizing agent and 1% retention aid, is added to the fiber suspension in such a way that an amount of 0.3% dry matter each of the sizing agent according to regulation A and the retention agent according to regulation D, based on the solids content of the Fibrous suspension arises. After processing the fiber suspension into paper, the sizing results given in Table 111 below are achieved:

Example 4: The sizing agent and the retention agent are added separately to the fiber suspension according to Example 3, which has a pH of 5.5. For this purpose a 25 _^0/0 strength, aqueous dispersion of the sizing agent according to Procedure A is prepared as indicated in Example 2. Fig. To the fiber suspension aqueous dispersion is first a 10 ^o / o-strength aqueous solution of retention agent according to Procedure D and 10 seconds thereafter, strength 25%, if the sizing agent such that an application amount of 0.3% of dry substance of the sizing and retention agent, based on the solids content of the fiber suspension. After processing the fiber suspension into paper as described in Example 1, the sizing results given in Table IV below are achieved:

Example 5: 100 parts of a liquid, commercially available, reinforced resin glue dispersion which has a dry matter content of 30% of reinforced tall resin (reinforcement with 6 to 8% fumaric acid) and a very high free resin content (of approx. 90%) are 500 Dilute parts of deionized water to a homogeneous, pourable, storage-stable dispersion. This diluted dispersion of the sizing agent is D mixed with 150 parts of a 10 ⁰ / o by weight aqueous solution of retention agent according to Procedure with stirring and then diluted with deionized water to give a formulation is produced containing 2% sizing agent and 1% retention agent, based on dry matter on sizing and retention agent and on the total weight of the formulation. Now the formulation for the fiber suspension according to Example 1 thus obtained, which has a pH of 7.8, is given such that an amount of 1% dry matter of the sizing agent and 0.5% of dry matter of the retention agent, based on the Solids content of the fiber suspension arises. The fiber suspension is then processed into paper as indicated in Example 1. The sizing results obtained are given in Table V below:

Example 6: The procedure is as described in Example 5, but the sizing agent and the retention agent are added separately to the fiber suspension. For this purpose, first the 10% aqueous solution of the retention agent according to regulation D and 10 seconds afterwards the diluted dispersion of the reinforced resin size specified in Example 5 for the fiber suspension according to Example 1, which has a pH of 7.8, given such that an amount of 1% dry matter of the sizing agent and 0.5% dry matter of the retention agent, based on the solids content of the fiber suspension, is used. The fiber suspension is then processed into paper as indicated in Example 1. The sizing results obtained are given in Table VI below.

Example 7: A liquid, commercially available, reinforced resin soap dispersion (rosin saponified, rosin present as root resin which is reinforced with about 11% maleic anhydride), which has a dry matter content of 50% and a free resin content of 4.5%, is included diluted 10 times the volume of water to a homogeneous, storage-stable dispersion. To the fiber suspension in accordance with Example 1, having a pH value of 7.8, a 10 ⁰ / o solution of retention agent according to Procedure D and 10 seconds is first then added the above-obtained dilute dispersion of the reinforced resin soap as a sizing agent such that an amount of dry matter of the sizing agent of 10% and dry matter of the retention agent of 0.5%, based on the solids content of the fibrous suspension, arises. The fiber suspension is then processed into paper as indicated in Example 1, the sizing results given in Table VII below being achieved:

Example 8: a commercially available 51 parts commercially as a Spanish gum rosin present rosin, having a dry matter content of 98%, are 2.5 parts of a condensation product of a naphthalenesulfonic acid and formaldehyde as dispersant, 250 parts of a 10 ⁰ / o by weight, aqueous solution of the retention aid according to regulation D and 196.5 parts of deionized water in the presence of glass beads with an average of 2 mm at room temperature. This gives 500 parts of a formulation which is in the form of a homogeneous, pourable and storage-stable dispersion and contains 10% rosin as a sizing agent and 5% retention agent, based on the dry matter of sizing and retention agent and on the total weight of the formulation.

To the fiber suspension in accordance with Example 1, having a pH value of 7.8, the resulting formulation will now be given so that a required quantity of dry substance of the sizing agent of 1% and the dry matter of the retention agent of 0.5 ^o / o, based on the solids content of the fiber suspension arises. The pulp suspension is then processed into paper as indicated in Example 1, the sizing results given in Table VIII below being achieved:

EXAMPLE 9 The procedure is as described in Example 8, but 50 parts of stearic acid (instead of 51 parts of rosin) are used as the sizing agent. The formulation of the sizing and retention agent obtained is likewise homogeneous, pourable and stable in storage and is added to the fiber suspension as indicated in Example 8. The sizing results of the paper produced from this fiber suspension are shown in Table IX below:

Claims (24)

1. Process for gluing paper or cardboard, characterized. that at least (A) an anionic, hydrophobic sizing agent and (B) a retention aid which is a polymerized, optionally modified, crosslinked monoallylamine of the formula

contains, wherein T CI, Br, I. HSO ₄ , HS0 ₃ , H ₂ P0 ₄ , H ₂ P0 ₃ , HCOO, CH ₃ COO or C ₂ H ₅ COO, z ₁ a number from 10 to 100,000 and _Z2 a Number from zero to 100,000 mean inserts. 2. The method according to claim 1, characterized in that for mass sizing of paper or cardboard, components (A) and (B) are added to aqueous, cellulose-containing, optionally filler-containing fiber suspensions in any order or simultaneously. 3. The method according to claim 1, characterized in that for surface sizing the paper is impregnated with an aqueous liquor containing the components (A) and (B) and dried. 4. The method according to any one of claims 1 to 3, characterized in that as component (A) a fatty acid, a resin size or a synthetic sizing agent, the at least one anionic, in salt form or acidic group and at least one hydrophobic alkyl or Alkenyl radical having 5 to 22 carbon atoms, is used. 5. The method according to any one of claims 1 to 3, characterized in that a cationic retention agent of the formula is used as component (B)

uses, wherein zi has the meaning given in claim 1. 6. The method according to claim 2, characterized in that one uses 0.3 to 6 percent by weight of the sizing agent (A) and 0.1 to 2 percent by weight of the retention aid (B), provided a fatty acid or resin size is used as the sizing agent. 7. The method according to claim 2, characterized in that one uses 0.02 to 3 percent by weight of the sizing agent (A) and 0.02 to 3 percent by weight of the retention aid (B), if a synthetic sizing agent is used. 8. The method according to claim 3, characterized in that the glue liquor is used in such a way that a surface application of dry substance of components (A) and (B) is produced on the treated paper from 50 to 200 mg / m ² . 9. Aqueous composition for performing the method according to claim 2, wherein the sizing agent (A) and the retention agent (B) are added simultaneously to the fiber suspension, characterized in that they (A) 2 to 40 weight percent sizing agent and (B) 0.1 to 20 percent by weight of retention aid, based in each case on dry matter of (A) and (B) and on the total weight of the aqueous composition, and if appropriate contains customary additives. 10. Aqueous glue liquor as a composition for performing the method according to claim 3, characterized in that it (A) 0.02 to 0.4 weight percent sizing agent and (B) 0.01 to 0.2 percent by weight of retention aid, based in each case on dry matter of (A) and (B) and on the total weight of the aqueous composition, and optionally contains customary additives. 11. Use of the combination of components (A) and (B) according to claim 1 for gluing paper or cardboard. Claims for the following contracting states: AT, ES 1. Process for gluing paper or cardboard, characterized in that at least (A) an anionic, hydrophobic sizing agent and (B) a retention aid which is a polymerized, optionally modified, crosslinked monoallylamine of the formula

contains, wherein T CI, Br, I. HSO ₄ , HSO ₃ , H ₂ PO ₄ . H ₂ P0 ₃ . HCOO, CH ₃ COO or C ₂ HsCOO, z _{1 is} a number from 10 to 10,000 and z _{2 is} a number from zero to 100,000. starts. 2. The method according to claim 1, characterized in that for mass sizing of paper or cardboard, components (A) and (B) are added to aqueous, cellulose-containing, optionally filler-containing fiber suspensions in any order or simultaneously. 3. The method according to claim 1, characterized in that for surface sizing the paper is impregnated with an aqueous liquor containing the components (A) and (B) and dried. 4. The method according to any one of claims 1 to 3, characterized in that a component (A) is a fatty acid. a resin size or a synthetic sizing agent which has at least one anionic, salted or acidic group and at least one hydrophobic alkyl or alkenyl radical having 5 to 22 carbon atoms. starts. 5. The method according to any one of claims 1 to 3, characterized in that a cationic retention agent of the formula is used as component (B)

uses, wherein zi has the meaning given in claim 1. 6. The method according to claim 2. characterized. that 0.3 to 6 percent by weight of the sizing agent (A) and 0.1 to 2 percent by weight of the retention agent (B) are used if a fatty acid or resin size is used as the sizing agent. 7. The method according to claim 2. characterized. that 0.02 to 3 percent by weight of the sizing agent (A) and 0.02 to 3 percent by weight of the retention agent (B) are used. if a synthetic sizing agent is used. 8. The method according to claim 3, characterized in that the glue liquor is used in such a way that a surface application of dry substance of components (A) and (B) is produced on the treated paper from 50 to 200 mg / m ² . 9. The method according to claim 2, characterized in that the fibrous suspension has a pH of 3.5 to 10, a Schopper-Riegler freeness of 10 to 60 "and a solids content of 0.1 to 5 percent by weight. 10. The method according to claim 3, characterized in that drying the paper at 60 to 140 ° C.