CZ2003371A3 - Paper sizing process - Google Patents

Abstract

The invention refers to an aqueous sizing dispersion comprising a sizing agent, starch having aromatic groups and a condensed sulfonate, wherein the starch contains less than 95 weight % of amylopectin and a method of sizing paper comprising adding an aqueous sizing dispersion to a cellulosic dispersion which has a conductivity of at least 0.5 mS/cm.

Description

Technical field

BACKGROUND OF THE INVENTION The present invention relates to a method for sizing paper comprising adding a sizing dispersion comprising a sizing agent and a polymer having one or more aromatic groups to a slurry containing cellulosic fibers and optionally fillers and a sizing promoter comprising a polymer having one or more aromatic groups. the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.

BACKGROUND OF THE INVENTION

Dispersions or emulsions of sizing agents are used in the manufacture of paper to obtain paper and board with improved resistance to moisture and penetration of various fluids. The sizing dispersions are usually added to an aqueous suspension containing cellulose fibers or additives. The aqueous suspension is fed to the filler and various headboxes, spraying the suspension onto a screen on which a web of paper is formed.

For example, starches are added to the slurry, and compounds such as fine particulate materials are usually added to facilitate dewatering of the slurry to the nets. The water drawn off the sieve, the so-called white water, is usually partially recycled to the papermaking process. The cellulosic suspension contains a certain amount of non-fibrous material such as fillers, electrically charged polymers, sizing agents, and various impurities and electric charges such as anionic residues, electrolytes, colloids, etc. Some of the non-fibrous material affects the sizing effect, which apparently worsens. High content • ·

compounds with an electric charge, such as a high salt content in the suspension, result in a suspension which is difficult to squeeze, i.e., in the form of a suspension. that the paper does not have satisfactory sizing properties. Other compounds present in the suspension that impair sizing are various lipophilic wood extracts, which may come from recycled fibers and so-called mechanical pulps. sizing agent often to higher costs and to water.

reagents in white high-yield pulp,

Increased amount of added improves sizing, but leads to increased accumulation of sizing

The accumulation of non-fibrous material and other components present in the slurry is even more pronounced in paper mills where white water is largely recirculated and where only small amounts of fresh water are fed to the paper production. It is therefore an object of the invention to further improve sizing. It is a further object of the present invention to improve sizing when applying sizing to cellulosic suspensions having a high conductivity and / or high content of lipophilic wood extracts. Other objects of the invention will become apparent below.

WO 99/55964 discloses a method of making paper in which dewatering and retention aids are added to a slurry containing cationic and amphoteric polysaccharides having a hydrophobic group. The polysaccharides may be used in conjunction with anionic fine particulate material and sizing agents.

WO 99/55965 relates to a papermaking process in which dewatering and retention means are added to a slurry containing a cationic organic polymer having an aromatic group. The cationic organic polymer is preferably used together with an inorganic fine particulate material.

US 6,001,166 discloses aqueous alkyldiketene dispersions comprising cationic starch and an anionic dispersing agent such as lignosulfonic acids, condensation products

naphthalenesulfonic acids and formaldehyde.

WO 9833979 discloses aqueous dispersions of a cellulose-reactive sizing agent comprising cationic organic compounds and anionic stabilizers.

SUMMARY OF THE INVENTION

Surprisingly, it has been found that the invention according to the claims improves sizing in general, in particular improves sizing of aqueous suspensions containing cellulosic fibers having high conductivity. More particularly, the invention relates to a method for sizing a paper, comprising adding a sizing dispersion comprising a sizing agent and a polymer having one or more aromatic groups, and a sizing promoter comprising a polymer having one or more aromatic groups formed to a slurry containing cellulosic fibers and optionally fillers. the suspension is shaped and dewatered, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.

The sizing agent included in the dispersion, according to the inventive method added to the suspension, may be any known sizing agent, such as, for example, non-cellulose-reactive agents, including resins, e.g., enriched and / or esterified resins, waxes, fatty acids and resin acid derivatives, e.g. fatty amides and fatty esters such as triesters of glycerin and natural fatty acids and / or cellulose-reactive agents. Preferably, the sizing agent comprises a cellulose-reactive sizing agent. The cellulose-reactive sizing agents contained in the sizing dispersion may be selected from any of the cellulose-reactive agents known in the art. The sizing agent is preferably

-4 is selected from the group consisting of hydrophobic ketene dimers, ketene multimers, acid anhydrides, organic isocyanates, carbamoyl chlorides and mixtures thereof, preferably ketene dimers and acid anhydrides, most preferably ketene dimers. Suitable ketene dimers have the general formula (I) below wherein R ¹ and R ² are saturated or unsaturated hydrocarbon groups, generally saturated hydrocarbon groups, preferably having from 8 to 36 carbon atoms, usually straight or branched chain alkyl groups having 12 to 12 carbon atoms. up to 20 carbon atoms, for example hexadecyl and octadecyl groups. The ketene dimers may be at a liquid ambient temperature, i.e. at 25 ° C, preferably at 20 ° C. The acid anhydrides can generally be characterized by the following general formula (II), wherein R ³ and R ⁴ may be the same or different and represent saturated or unsaturated hydrocarbon groups, preferably containing. C 8 to 30 carbon atoms, or R ³ and R ⁴ together with the -COC- group form a 5 to 6-membered ring, optionally further substituted by a hydrocarbon group containing up to 30 carbon atoms. Examples of acid anhydrides that are commercially used include alkyl- and alkenylsuccinic anhydrides, especially isooctadecenylsuccinic anhydride.

(I) R ^{1 -} CH = C - CH - R ² o - c = o (II) oo, ¹ '4

R ³ —C — O — C — R ⁴

Suitable ketene dimers, acid anhydrides and organic isocyanates include the organic compounds disclosed in U.S. Patent 4,522,686, which is incorporated herein by reference. Examples of suitable carbamoyl chlorides include those disclosed in U.S. Patent 3,887,427, which is also incorporated herein by reference.

The sizing dispersion added to the slurry may have a sizing agent content of 0.1 to 50 wt% based on the total amount of the dispersion / emulsion, preferably more than 20 wt%. Dispersions containing ketene dimer as sizing • · · · · ·

the agent may have a ketene dimer content of 5 to 50 wt% based on the dispersion as a whole, preferably 10 to 35 wt%. The dispersion or emulsion containing an acid anhydride as the sizing agent may have an acid anhydride content of 0.1 to 30% by weight, preferably 1 to 20% by weight, based on the total weight of the dispersion / emulsion. Dispersions containing non-cellulose-reactive sizing agents preferably have a sizing agent content of 5 to 50% by weight, preferably 10 to 35% by weight. A polymer having one or more aromatic groups, eg, an anionic and cationic polymer having one or more aromatic groups, contained in the sizing dispersion, is preferably present in an amount of about 0.1 to about 15% by weight, based on the sizing agent.

The amount of sizing agent added to the cellulosic fiber-containing aqueous suspension may be 0.01 to 5% by weight, preferably 0.05 to 1.0% by weight, based on the dry weight of the cellulose fibers and optionally fillers, the dosage being dependent on the quality of sizing pulp or paper, the sizing agent, or the sizing intensity.

The sizing dispersion comprising a polymer containing at least one aromatic group may be anionic or cationic, i.e. a. the dispersing and / or stabilizing agent present in the dispersion, i.e. the diperging system, may be generally anionic or cationic. The dispersion system may include any dispersion or emulsion facilitating agent, for example, a dispersing and / or stabilizing agent consisting of a polyelectrolyte, a surfactant, and an electrolyte. Anionic aqueous sizing dispersions may include cationic compounds, eg, cationic polyelectrolytes (cationic or amphoteric polyelectrolytes with a total cationic charge) and / or cationic surfactants and / or other cationic compounds known to those skilled in the art, provided that the entire dispersing system is anionic. On the other hand, cationic water sizing

dispersions may contain anionic compounds, i.e. anionic polyelectrolytes (anionic or amphoteric polyelectrolytes with a total anionic charge) and / or anionic surfactants and / or other anionic compounds known to the person skilled in the art, provided that the entire dispersing system is anionic. The anionic or cationic charge of the sizing dispersion can be determined using a ZetaMaster S, type PCS.

The invention provides a method wherein a sizing dispersion comprising a sizing agent and a polymer having one or more aromatic groups and a sizing promoter comprising a polymer having one or more aromatic groups are added to an aqueous suspension containing cellulosic fibers and optionally fillers, wherein the sizing dispersion and the sizing the promoter is added separately to the aqueous suspension. A polymer having one or more aromatic groups may or may not have an electric charge, preferably it has an electric charge, i.e. an electric charge. the polymer may be cationic or anionic, for example it may be amphoteric and may have a total (pure) anionic or cationic charge. The polymer may be an organic polymer, preferably derived from natural materials such as polysaccharides, eg starch, guar gum, cellulose, chitin, chitosan, glycans, galactans, glucans, xanthan gum, pectin, mannan, dextrin, preferably starches and guar suitable starches include potato, cereal, wheat, tapioca, rice, corn, barley, etc., or also a synthetic polymer such as chain polymerized polymers, e.g., vinyl addition polymers such as acrylate, acrylamide and vinylamide based polymers, and sequentially polymerized polymers such as polyurethanes. Preferably, the organic of the polysaccharides, for example starches and polymers, is selected from vinyl addition polymers such as acrylamide-based polymers.

Aromatic group of polymer can be present in the main • to this *

Or, preferably, the aromatic group may be formed by a side group attached to the backbone or extending the backbone, or may be present in a side group attached to the backbone, or extending the main chain. The polymer is preferably an organic polymer having a totally anionic or cationic charge.

The sizing promoter further comprises another polymer having one or more aromatic groups which may be any of the above polymers. The total charges of the two polymers containing at least one aromatic group contained in the sizing promoter are the opposite, usually added separately to the aqueous suspension. Preferably, the polymer or both polymers contained in the sizing promoter have an aromatic group, provided that the polymer (s) do not contain melamine or melamine derivatives.

containing groups, and

According to the invention, the sizing dispersion, a polymer having one or more aromatic sizing promoters comprising a first polymer having one or more aromatic groups and optionally another second polymer having one or more aromatic groups, is separately added to the aqueous suspension. By separate addition is meant that the sizing dispersion and the sizing promoter are added to the cellulosic suspension (pulp) at different locations or substantially at the same site, but separately in time. Further, if the sizing promoter comprises two polymers having aromatic groups, they are also preferably added separately.

A preferred embodiment of the invention relates to a method for sizing paper, wherein a sizing dispersion comprising a polymer having one or more aromatic groups, preferably a cationic organic polymer having one or more aromatic groups and / or anionic, is added to an aqueous suspension containing cellulosic fibers and optionally fillers. a polymer having one or more aromatic groups, wherein the three tiers of the three tiers of the tiers are

An organic polymer having groups such as a polysaccharide or wherein the anionic anionic polymer is a sequentially polymerized polymer, a polysaccharide, or a natural aromatic polymer, preferably is an anionic polymer having aromatic groups sequentially polymerized polymer or natural aromatic polymer; and wherein the sizing promoter comprises a polymer having one or more aromatic groups which is a cationic one or more aromatic cationic cationic vinyl addition polymer, and the polymer having one or more aromatic groups is a sequentially polymerized polymer, polysaccharide or natural aromatic polymer, preferably sequentially polymerized polymer or a natural aromatic polymer such as a naphthalene sulfonate condensation polymer, a polystyrene sulfonate polymer, or a modified lignin polymer, the formed suspension being shaped and dewatered, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.

According to a preferred embodiment of the invention, in the method of sizing paper to an aqueous suspension comprising cellulosic fibers and optionally fillers, a sizing dispersion comprising a sizing agent, a cationic organic polymer having one or more aromatic groups and / or an anionic polymer having one or more aromatic groups is added, wherein the anionic the polymer is a sequentially polymerized polymer, polysaccharide, or natural aromatic polymer, preferably, the anionic polymer having one or more aromatic groups is a sequentially polymerized polymer or natural aromatic polymer; and wherein the sizing promoter comprises a cationic organic polymer having one or more aromatic groups and an anionic polymer having one or more aromatic groups selected from the group consisting of sequentially polymerized polymers, polysaccharides and natural aromatic polymers, the formed suspension being shaped and dewatered, wherein:

The sizing dispersion and the sizing promoter are added separately to the aqueous suspension.

According to yet another preferred embodiment of the invention, in the method of sizing paper to an aqueous suspension comprising cellulosic fibers and optionally fillers, a sizing dispersion comprising a sizing agent and an anionic polymer having one or more aromatic groups is added, wherein the anionic polymer is sequentially polymerized polymer, polysaccharide or natural aromatic polymer, wherein the amount of sizing dispersion added to the slurry is about 0.01 to about 5.0 wt%, calculated as the sizing agent based on dry fibers, and wherein the sizing promoter comprises a cationic polymer having one or more aromatic groups, preferably a cationic polysaccharide or a cationic vinyl addition polymer, more preferably a cationic polysaccharide, and an anionic polymer having one or more aromatic groups which is a sequentially polymerized polymer, a polysaccharide, or a natural aromatic polymer, wherein the amount of cationic polymer added to the suspension is about 0.001 to about 3% by weight, based on dry fibers, and wherein the amount of anionic polymer added to the suspension is about 0.001 to about 3% by weight, based on dry fibers, the suspension formed is shaped and The sizing dispersion and the sizing promoter are added separately to the aqueous suspension.

According to a further preferred embodiment of the invention, in the method of sizing paper to an aqueous suspension comprising cellulose fibers and optionally fillers, a sizing dispersion comprising a sizing agent, a cationic organic polymer having one or more aromatic groups, such as a cationic polysaccharide or cationic vinyl addition polymer, is preferably added. a cationic polysaccharide, and an anionic polymer having one or more aromatic groups, wherein the anionic polymer is

sequentially polymerized polymer, polysaccharide or natural aromatic polymer, wherein the amount of sizing dispersion added to the slurry is about 0.01 to about 5.0% by weight, calculated as a sizing agent based on dry fibers, and wherein the sizing promoter comprises a cationic polymer having one or more; a plurality of aromatic groups, preferably a cationic polysaccharide or cationic vinyl addition polymer, more preferably a cationic polysaccharide, and an anionic polymer having one or more aromatic groups which is a sequentially polymerized polymer, polysaccharide or natural aromatic polymer, wherein the amount of cationic polymer added to the suspension is about 0.001 to about 3% by weight, based on dry fibers, and wherein the amount of anionic polymer added to the suspension is about 0.001 to about 3% by weight, based on dry fibers, the formed suspension is shaped and dewatered, wherein the sizing dispersion and the sizing promoter is added separately to the aqueous suspension.

According to yet another embodiment of the invention, in the method of sizing paper to an aqueous suspension comprising cellulosic fibers and optionally fillers, a sizing dispersion comprising a sizing agent such as a cellulose-reactive sizing agent and a cationic organic polymer having an aromatic group and / or anionic polymer having an aromatic group selected from the group consisting of sequentially polymerized polymers, polysaccharides or natural aromatic polymers, and a sizing promoter comprising a cationic polysaccharide having the general structural formula (I):

R 1 (O 1 X 'p __ (_ _A - N ⁺ - R ₂ ) _n

I r ₃ • φ

wherein Ρ is a polysaccharide residue; Ά is a chain containing C and H atoms, connecting N to the polysaccharide residue, R x and R ₂ represent H or a hydrocarbon group, R ₃ is an aromatic hydrocarbon group, n is an integer from 2 to 300 000, and X is an anionic counterion;

or a vinyl addition polymer obtained by polymerizing a cationic monomer or a monomer mixture containing a cationic monomer of the general formula (II)

CH ₂ = C-R 1 R ₂ (> ^j ) ih

O = c — a — Bi — N — Q x .....

AND

Ra wherein R 1 is H or CH ₃ ; R ₂ and R ₃ are alkyl groups having 1 to 3 carbon atoms, Αχ is O or NH, B 1 is an alkylene group having 2 to 8 carbon atoms or a hydroxypropylene group, Q is a substituent containing an aromatic group, and X is an anionic counterion;

and an anionic polymer having one aromatic group which is a sequentially polymerized polymer, a polysaccharide, or a natural aromatic polymer.

According to yet another preferred embodiment of the invention, in the method of sizing paper to an aqueous suspension comprising cellulosic fibers and optionally fillers, a sizing dispersion comprising a sizing agent, a cationic organic polymer having an aromatic group and / or an anionic polymer having an aromatic group selected from sequentially polymerized polymers is added. , polysaccharides or natural aromatic polymers, preferably the anionic polymer having the aromatic group is a sequentially polymerized polymer or natural aromatic polymer, and a sizing promoter comprising a cationic polysaccharide having the general structural formula (I):

• · φ ·

- 12Ri (Ο

I X

Ρ - (- A - Ν ⁺ —R ₂ ) _n r

r ₃ where P is a polysaccharide residue; A is a chain comprising C and H atoms, connecting N to the polysaccharide residue, R 1 and R ₂ represent H or a hydrocarbon group, R 3 is an aromatic hydrocarbon group, n is an integer of 2 to 300 000, and X - is an anionic counterion;

and an anionic polymer having one aromatic group which is a sequentially polymerized polymer, a polysaccharide, or a natural aromatic polymer, wherein the sizing dispersion. and the sizing promoter are added separately to the aqueous suspension.

According to yet another preferred embodiment of the invention, in the method of sizing paper to an aqueous suspension comprising cellulosic fibers and optionally fillers, a sizing dispersion comprising a sizing agent, a cationic organic polymer having an aromatic group and / or an anionic polymer having an aromatic group selected from sequentially polymerized polymers is added. , polysaccharides or natural aromatic polymers, and a sizing promoter comprising a cationic vinyl addition polymer obtained by polymerizing a cationic monomer or a monomer mixture comprising a cationic monomer of the general formula (II)

_CH2 --C - R 1 R ₂ (II): I ₊ L. '

O = C - Al - Bt - N - Q X

R ₃

Wherein R 1 is H or CH ₃ ; R ₂ and R ₃ are alkyl groups having 1 to 3 carbon atoms, Aj is O or NH, Bi is an alkylene group having 2 to 8 carbon atoms or a hydroxypropylene group, Q is a substituent containing an aromatic group,. a. X ~. is an anionic counterion;

and an anionic polymer having an aromatic group selected from sequentially polymerized polymers, polysaccharides or natural aromatic polymers, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.

The anionic polymer having one or more aromatic groups (contained in the promoter and / or dispersion, preferably the promoter) is preferably selected from the group consisting of sequentially polymerized polymers, polysaccharides or natural aromatic polymers, provided that the anionic polymer is not a melamine sulfonic acid condensation polymer. . The anionic polymer is usually selected from naphthalene sulfonate condensation polymers, such as condensed naphthalene sulfonates, polystyrene sulfonate polymers, or modified lignin polymers, such as lignosulfonate. Most preferably, the anionic polymer is a fused naphthalene sulfonate or lignosulfonate.

According to the invention, the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. Although the sizing dispersion may contain the same polymers as those present in the sizing promoter, a substantial improvement in sizing can only be observed if the sizing promoter and the sizing dispersion are added to the aqueous suspension separately. Separate addition is understood to mean that the sizing dispersion, which may comprise any of the sizing promoter polymers and the sizing promoter, is added to the papermaking line at different locations or substantially at the same site, but over time. separately. Further, the cationic organic polymer and the anionic polymer forming the sizing

999 9

• 9 • 9 • 9 • • 9 9 99 ·· • 9 9 · 9 9 9 9 9 9 9 • 9 • 9 9 9 • · • · · 9 9 9

the promoter is also preferably added separately. Preferably, the anionic polymer having the aromatic group contained in the sizing promoter is added to the suspension after the sizing dispersion and the cationic organic polymer.

Cationic polymer

The cationic organic polymer having one or more aromatic groups, which is present in the sizing promoter and which may also be included in the sizing composition, may be derived from natural or synthetic materials, and may be linear, branched or crosslinked. Preferably, the cationic polymer is water-soluble or dispersible. Examples of suitable cationic polymers are cationic polysaccharides, for example starches, guar gum, cellulose, chitin, chitosan, glycans, galactans, glucans, xanthan gum, pectin, mannan, dextrin, preferably starches and guar gum, wherein suitable starches include potato, cereal, wheat, tapioca, rice, maize, barley, etc .; cationic synthetic organic polymers such as chain polymerized polymers, e.g., cationic vinyl addition polymers such as acrylate, acrylamide and vinylamide based polymers, and sequentially polymerized polymers, such as polyurethanes. Preferably, the organic polymers are selected from polysaccharides, for example starches and vinyl addition polymers, such as aromatic groups having acrylamide-based polymers.

The aromatic group of the cationic organic polymer may be present in the polymer backbone, or in a substituent attached to or backbone extending the backbone, preferably in a substituent. Examples of suitable aromatic groups include aryl, arylalkyl and alkylaryl groups such as phenyl, phenylene, naphthyl, xylylene, benzyl and phenylethyl; preferably benzyl, nitrogen-containing aromatic (aryl) groups such as a pyridine or quinoline group and derivatives thereof. Examples of cationically charged groups that may be present in the cationic polymer as well as in the monomers used to prepare the cationic polymer include quaternary ammonium groups, tertiary amino groups, and acid addition salts thereof.

According to a preferred embodiment, the cationic organic polymer having an aromatic group is selected from cationic polysaccharides. The aromatic group of polysaccharides may be attached to heteroatoms such as nitrogen or oxygen present in the polysaccharides, and the heteroatom may bear charge, for example when it is nitrogen. The aromatic group may also be attached to a heteroatom containing group, eg, an amide, ester or ether group, which groups may be attached to the polysaccharide backbone, for example, through an atomic chain. Examples of suitable aromatic and aromatic-containing groups include aryl and alkyl groups such as phenyl, phenylene, naphthyl, phenylene, xylylene, benzyl and phenylethyl; nitrogen-containing aromatic (aryl) groups such as pyridine and quinoline groups, as well as derivatives thereof, wherein one or more substituents attached to said aromatic groups may be selected from the group consisting of a hydroxyl group, a halide such as chloride, nitro and hydrocarbon groups having 1-4 carbon atoms.

The cationic organic polymer is preferably selected from cationic polysaccharides having the general structural formula (I):

• ·

Ri (I) I. *, r ₃ wherein P is a polysaccharide residue; A is a group attaching N to a polysaccharide residue, preferably a chain comprising C and H atoms, optionally O and / or N atoms, usually an alkylene group of 2 to 18, preferably 2 to 8 carbon atoms, optionally interrupted or substituted with one or more heteroatoms , e.g., O or N, e.g., alkyleneoxy or hydroxypropylene -CH 2 -CH (OH) -CH ₂ -; R1 and R2 are both H or preferably a hydrocarbon group, preferably alkyl having 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms; R 3 is preferably an aromatic hydrocarbon group, for example an arylalkyl-phenylethyl group; n j <

300,000, preferably from 5,000 to 125,000, or alternatively an aromatic group, comprises an anionic counterion, generally a halide, for example chloride.

pina, e.g. benzyl and whole number from about 2 to about 200 000, preferably from 6 to i <R2 and R 3 together with N form 5 to 12 carbon atoms; and X ' Yippee

The aromatic-modified cationic polysaccharides may have a variety of degrees of substitution; the degree of cationic substitution (DS _C ) may be 0.01 to 0.5, preferably 0.02 to 0.3, most preferably 0.025 to 0.2, the degree of aromatic substitution (DS _flr ) may be 0.01 to 0.5 , preferably 0.02 to 0.3, most preferably 0.025 to 0.2, and the degree of anionic substitution (DS _ft ) may be 0 to 0.2, preferably 0 to 0.1, most preferably 0 to 0.05.

The polysaccharides may be prepared by subjecting the polysaccharide to cationic and aromatic modification in a known manner using one or more agents containing a cationic group and / or an aromatic group, for example

- 17 alkali or metal non-ionic,,

• 4 44

4 4

4ti

4 4

By reacting the agent with a polysaccharide in the presence of a substance such as an alkaline earth alkali hydroxide. The polysaccharides to be cationic and aromatic modified may be anionic, amphoteric or cationic. Suitable modifying agents include nonionic agents such as arylalkyl halides such as benzyl chloride and benzyl bromide; the reaction products of epichlorohydrin and dilakylamine having at least one substituent containing an aromatic group as defined above, for example 3-dialkylamino-1,2-epoxypropane; and cationic agents such as the reaction products of epichlorohydrin and a tertiary amine having at least one substituent containing an aromatic group as defined above, for example dimethylbenzylamine; arylamines such as pyridine and quinoline. Suitable cationic agents of this type include 2,3-epoxypropyltrialkylammonium halides and halohydroxypropyltrialkylammonium halides such as N- (3-chloro-2-hydroxypropyl) -N- (hydrophobic alkyl) -N, N-di (lower alkyl) ammonium chloride and N-glycidyl- N- (hydrophobic alkyl) -N, N-di (lower alkyl) ammonium chloride, wherein the aromatic group is as defined above, namely octyl, decyl and dodecyl, and the lower alkyl is methyl or ethyl; and halohydroxypropyl-N, N-dialkyl-N-alkylarylammonium halides, and N-glycidyl-N- (alkylaryl) -N, N-dialkylammonium chloride, e.g. N- (3-chloro-2-hydroxypropyl) -N- (alkylaryl) -N, N-di (lower alkyl) ammonium chloride wherein the alkylaryl and lower alkyl groups are as defined above, especially N- (3-chloro-2-hydroxypropyl) -N-benzyl-N, N-dimethylammonium chloride; and N- (3-chloro-2-hydroxypropyl) pyridinium chloride. Generally, using a non-ionic flavoring agent, the polysaccharide is suitably converted to cationic before or after hydrophobic modification by any of the cationic agents known in the art. Examples of suitable cationic and / or aromatic modifying agents, aromatic group-modified polysaccharides and methods for their preparation include those described in the patents.

4,687,519 and 5,463,127; . in International Patent Application WO 94/24169, in Patent Application EP 189 935, and in SPPatel, RGPatel and VSPatel, Starch / Stark 41 (1989), No. 5, pp. 192-196, the entire contents of which are incorporated herein by reference. by reference incorporate e.

According to another preferred embodiment, the cationic organic polymer is selected from homopolymers α. copolymers prepared from one or more monomers comprising at least one monomer having an aromatic group, preferably an ethylenically unsaturated monomer. The cationic polymer may be linear or branched. The aromatic group of the cationic polymer may be present in the polymer backbone, or preferably the aromatic group may be a backbone attached to or backbone extending, or may be present in a backbone attached or backbone extending. The aromatic (aryl) group may be an optionally substituted phenyl group, an optionally substituted naphthyl group, for example a group having the formula -CgH ₅ -, -C ₆ H ₄ -, -C ₆ H ₃ - and -C ₆ H ₂ -, eg phenylene -C ₆ H ₅ -, xylylene - CH ₂ —C ₆ H ₄ - CH ₂ -, phenyl -C ₆ H ₅ -, benzyl -CH ₂ -C ₆ H ₅ , phenylethyl-CH ₂ CH ₂ -C ₆ H ₅ , and substituted phenyl (e.g. -C ₆ H ₄ Y, -C ₆ H ₃ Y _2, and -ΟδΗ ₂ Υ ₃ , wherein one or more substituents Y attached to the phenyl ring may be selected from the group consisting of hydroxyl, halide, e.g. chloride, nitro and hydrocarbyl having 1 to 4 carbon atoms.

The cationic polymer is preferably a vinyl addition polymer. The term vinyl addition polymer, as used herein, means a polymer prepared by the addition polymerization of one or more vinyl monomers or ethylenically unsaturated monomers, for example acrylamide-acrylate-based monomers. The cationic polymer is preferably a cationic vinyl addition polymer obtained by cationic polymerization.

«* 99 • · · · · · · · · ·

9 · · · · ·

Of a monomer or monomer mixture containing a cationic monomer corresponding to the general formula (II)

CH ₂ = C ₄ R ₄ r ₂ 00

.. I l ₊ ·. ·. ·· ·. : ·· ··

O = C - A - B ₄ - N - QX, -j R ₃ , R, wherein R 1 is H or CH 2; R ₂ and R 3 are alkyl groups having 1 to 3 carbon atoms, usually 1 to 2 carbon atoms; A is O or NH; Bi is an alkylene group having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, or a hydroxypropylene group; Q is a substituent containing an aromatic group, preferably a phenyl or substituted phenyl group, which may be attached to the nitrogen via an alkylene group having generally 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, preferably Q is a benzyl group -CH ₂ - CgH5; and X is an anionic counterion; generally chloride. Examples of suitable monomers of formula (II) include quaternary monomers obtained by treating dialkylaminoalkyl (meth) acrylates, e.g. (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide, with benzyl chloride. Preferred cationic monomers of formula (II) include the quaternary salt of dimethylaminoethyl acrylate and benzyl chloride and the quaternary salt of dimethylaminoethyl methacrylate and benzyl chloride.

The cationic vinyl addition polymer may be a homopolymer made from a cationic monomer having an aromatic group or a copolymer made from a monomer mixture containing a cationic monomer having an aromatic group.

or one or more copolymerizable monomers. Suitable copolymerizable non-ionic polymers include monomers of formula (III)

CH ₂ —C - FU Rs O ¹¹ )

O == C— A ₂ - B ₂ - N

Wherein R ₄ is H or CH 3; R 5 and R 6 represent H or a hydrocarbon group, preferably an alkyl group having 1 to 6, preferably 1 to 4 and usually 1 to 2 carbon atoms; A ₂ is O or NH; B ₂ is an alkylene group having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, or a hydroxypropylene group, or alternatively A and B are absent and there is a single bond between C and N (O 2 C-NR 5 R 8). Examples of suitable copolymerizable monomers of this type include (meth) acrylamide; acrylamide-based monomers such as N-alkyl (meth) acrylamides and N, N-dialkyl (meth) acrylamides such as Nn-propyl acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide and N-tert-butyl (meth) acrylamide; and dialkylaminoalkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide; acrylate-based monomers such as dialkylaminoalkyl (meth) acrylates, e.g. and vinylamides, e.g.

N-vinylformamide and N-vinylacetamide. Preferred copolymerizable non-ionic monomers include acrylamide and methacrylamide, i. (meth) acrylamide, and the main polymer is preferably an acrylamide-based polymer.

Suitable copolymerizable cationic monomers include monomers of formula (IV).

-21 9 9 9 «« · · · · 9 4 «·

X (iv) and R 10 are H or preferably alkyl having 1 to 2 carbon atoms; Ai is O ch ₂ = c - R ₇ r ₈

O = C - A ₃ - β ₃ - N ⁺ - R ₁₀

I R ₉ wherein R 7 is H or CH _3; R ₈ , R ₉ preferably a hydrocarbon group, up to 3 carbon atoms, generally 1 or NH; B ₃ is an alkylene group having 2 to 4 carbon atoms, preferably 2 to 4 carbon atoms, or a hydroxypropylene group, and X is an anionic counterion, usually methyl sulfate or a halide, for example chloride. Examples of suitable cationic copolymerizable monomers include acid addition salts and quaternary ammonium salts of the dialkylaminoalkyl (meth) acrylate and the dialkylaminoalkyl (meth) acrylaramides listed above, generally prepared using acids such as HCl, H ₂ SO ₄ etc., or quaternizing agents such as methyl chloride , dimethylsulfate, etc., and dialyldimethylammonium chloride. Preferred copolymerizable cationic monomers include the quaternary salt of dimethylaminoethyl (meth) acrylate methyl chloride and dialyldimethylammonium chloride. Also copolymerizable anionic monomers such as acrylic acid, methacrylic acid, various sulfonated vinyl addition monomers, etc. may be used, preferably in smaller amounts.

The cationic vinyl addition polymer can be made from a monomer mixture usually containing 1 to 99 mol%, preferably 2 to 50 mol%. and preferably 5 to 20 mol%. a cationic monomer having an aromatic group, preferably corresponding to the general formula (II), and 99 to 1 mol%, preferably 98 to 50 mol%, preferably 95 to 80 mol%. a further copolymerizable monomer, which preferably comprises acrylamide or methacrylamide (i.e. (meth) acrylamide), wherein the monomer mixture preferably comprises 98 to 50 mol%, preferably · · · · · · · · · · · · · · · · · · · · · ·

-22 to 80 mol%. (meth) acrylamide, the sum of the percentages being 100.

The cationic polymer may also be selected from polymers produced by the condensation reaction of one or more aromatic group-containing monomers. Examples of such monomers include toluene diisocyanate, bisphenol A, phthalic acid, phthalic anhydride, etc., which can be used to produce cationic polyurethanes, cationic polyamidamines, etc.

Alternatively, the cationic polymer may be a polymer subjected to aromatic modification by means of an aromatic group containing agent. Suitable modifying agents of this type include benzylchloride, benzyl bromide, N- (3-chloro-2-hydroxypropyl) -N-benzyl-N, N-dimethylammonium chloride, and N- (3-chloro-2-hydroxypropyl) pyridinium chloride. Suitable polymers for such aromatic modification include vinyl addition polymers. If the polymer contains a tertiary nitrogen that can be quaternized with a modifying agent, the use of such a reagent usually results in the polymer becoming cationic. Alternatively, the polymer to be subjected to aromatic modification may be a cationic polymer, for example a cationic vinyl addition polymer.

Typically, the charge density of the cationic polymer is in the range of 0.1 to 6.0 meq / g dry polymer, preferably 0.2 to 4.0 and preferably 0.5 to 3.0. The weight average molecular weight of the synthetic polymer is usually at least 500,000, preferably more than about 1,000,000, and preferably 2,000,000. The upper limit is not critical, it may be about 50,000,000, usually 30,000,000, and preferably 25,000,000.

Anionic polymer

An anionic polymer having one or more aromatic groups contained in a sizing promoter, which may be

Is present in the sizing dispersion and is selected from the group consisting of sequentially polymerized polymers, polysaccharides, and natural aromatic polymers. The term sequentially polymerized polymer, as used herein, means a polymer obtained by sequential polymerization, also referred to as a step polymerization reaction. The anionic polymer preferably has an aromatic group provided that the anionic polymer is not a condensation polymer of melamine sulfonic acid. The anionic polymer may be a sequentially polymerized polymer or a natural polymer. The anionic polymers of the invention may be linear, branched or crosslinked. Preferably, the anionic polymer is a water-soluble or water-dispersible polymer. The anionic polymer is preferably organic.

Preferred anionic naphthalene sulfonate aromatic polymers are condensation polymers, polystyrene sulfonate polymers or modified lignin polymers, more preferably naphthalene sulfonate condensation polymers such as modified lignin sulfonate.

for example, condensation naphthalene sulfonate, and lignin polymers such as

The aromatic group of the anionic polymer may be present in the polymer backbone, or it may be in a substituent group attached to the polymer backbone. Examples of suitable aromatic groups include the aryl, arylalkyl and alkylaryl groups and derivatives thereof, tolyl, naphthyl, phenylene, xylylene, benzyl, derivatives of these groups. Examples of anionic charged groups that may be present in the anionic polymer as well as in the monomers used to prepare the anionic polymer include groups that carry an anionic charge and acid groups that carry an anionic charge upon dissolution or dispersion in water, which groups are summarized herein they are called anionic groups such as phenyl, phenylethyl and

For example, phosphates, phosphonates, sulfates, sulfonic acids, sulfonates, carboxylic acids, carboxylates, alkoxides, and phenolic groups; hydroxyl-substituted phenyl and naphthyl groups. The groups that carry the anionic charge are usually alkali metal, alkaline earth metal or ammonium salts.

Examples of suitable anionic sequentially polymerized polymers of the invention include condensation polymers, i. polymers obtained by sequential condensation polymerization, eg, condensation products of an aldehyde, eg formaldehyde, with one or more aromatic compounds containing one or more anionic groups, in particular polymers of the condensed naphthalene sulfonate type, and optionally with other comonomers useful in condensation polymerization, for example urea. Examples of suitable aromatic compounds containing anionic groups are phenolic and naphtholic compounds, e.g. phenol, naphthol, resorcinol and derivatives thereof, aromatic acids and their salts, e.g. phenyl, phenolic, naphthylic and naphtholic acids and salts, usually sulfonic acids and sulfonates, e.g. benzenesulfonic and benzenesulfonates, xylenesulfonic acid and xylenesulfonates, naphthalenesulfonic acid and naphthalenesulfonates, phenolsulfonic acid and phenolsulfonates.

Examples of other polymerized polymers suitable for anionic sequential use according to the invention include addition polymers, i. polymers obtained by sequential addition polymerization, eg anionic polyurethanes prepared from a mixture of monomers containing aromatic isocyanates and / or aromatic alcohols. Examples of suitable aromatic isocyanates include diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate and diphenylmethane-4,4'-diisocyanate. Examples of suitable aromatic alcohols include dibasic alcohols.

-25 bisphenol A, phenyldiethanolamine, and trimethylolpropane monoterephthalate.

ie, diols, e.g., glycerin monoterephthalate

Monohydric aromatic alcohols such as phenol and derivatives thereof may also be used. The monomer mixture may also contain non-aromatic isocyanates and / or alcohols, usually diisocyanates and diols, for example some of those used in the production of polyurethanes. Examples of monomers containing anionic groups monoester products of the reaction of trioles, trimethylolethane, trimethylolpropane and suitable include, for example, glycerol, with dicarboxylic acids or anhydrides thereof, e.g. trimethylol propane monosuccinate, trimethylol propane monoterephthalate, N, N-bis- (hydroxyethyl) glycine, di- (hydroxymethyl) propionic acid, N, N-bis- (hydroxyethyl) -2-aminoethanesulfonic acid and the like, optionally and usually in combination with a base, for example with an alkali metal or alkaline earth metal hydroxide such as sodium hydroxide, ammonia or an amine such as triethylamine forming the counterion.

Examples of suitable anionic chain polymerized polymers of the invention include anionic vinyl addition polymers obtained from a mixture of vinyl or ethylenically unsaturated monomers containing at least one monomer having an aromatic group and at least one monomer having an anionic group, generally copolymerized with nonionic monomers, for example acrylate and acrylamide . Examples of suitable anionic monomers include (meth) acrylic acid and paravinylphenol (hydroxystyrene).

Examples of suitable anionic polysaccharides are starches, guar gum, cellulose, chitin, chitosan, glycans, galactans, glucans, xanthan gum, pectin,

mannan, dextrin, preferably starches, guar gum and cellulose derivatives, and suitable starches include potato, cereal, wheat, tapioca, rice, corn and barley, preferably potato. The anionic groups in the polysaccharides may be natural and / or introduced by chemical processing. The aromatic groups in the polysaccharides may be introduced by chemical procedures known in the art.

Examples of suitable (modified) natural aromatic anionic polymers of the invention include kraft lignin, for example modified lignin polymers such as lignin adducts copolymerized with formaldehyde and sulfonated lignin, eg lignin sulfonate, and tannin extract, i.e., natural polyphenol substances found in organic extracts of bark and some types of wood.

The weight average molecular weight of the anionic polymer may vary within wide limits depending upon, inter alia, the type of polymer used and is generally at least about 500, preferably more than about 2000, suitably more than about 5000. The upper limit is not critical, it may be about 200,000 000, generally 150 000 000, preferably 100 000 000 and preferably 1 000 000.

The anionic polymer may have a degree of anionic substitution (DS _A ) within wide limits, depending on, inter alia. the type of polymer used; DS _A is generally 0.01 to 2.0, preferably 0.02 to 1.8, most preferably 0.025 to 1.5; and the degree of aromatic substitution (DSq) may be 0.001 to 1.0, generally 0.01 to 0.8, preferably 0.02 to 0.7 and preferably 0.025 to 0.5. In the case where the anionic polymer contains cationic groups, the degree of cationic substitution DS _C may be, for example, 0 to 0.2, preferably 0 to 0.1 and preferably 0 to 0.05, the anionic polymer having an overall anionic charge. Generally, the anionic charge density of the anionic polymer is in the range of 0.1 to 6.0 meq / g dry polymer, preferably 0.5 to 5.0 and preferably 1.0 to 4.0.

The cationic organic polymer having an aromatic group and the anionic polymer having an aromatic group contained in the sizing promoter may be added to the aqueous suspension (pulp) in any order separately from the addition of the sizing dispersion and in amounts that may vary within wide limits depending upon, inter alia. on the pulp type, salt content, salt type, filler content, type of filler, point of addition, etc. Generally, the polymers are added in an amount that provides better sizing than is achieved when none are added, and typically the cationic organic polymer is added to the pulp before by adding an anionic polymer. The cationic polymer is generally added in an amount of at least 0.001% by weight, preferably at least 0.005% by weight, based on the dry weight of the pulp, while the upper limit is typically 3% by weight, preferably 2% by weight. %, preferably at least 0.005% by weight, based on the dry weight of the stock, while the upper limit is generally 3% by weight, preferably 1.5% by weight.

In addition to the cationic organic polymer and the anionic polymer, the sizing promoter may contain other compounds that improve the sizing efficiency, such as an anionic fine particulate material, e.g., silica based particles and smectite type clays, low molecular weight cationic organic polymers, aluminum compounds such as alum, aluminates aluminum chloride, aluminum nitrate, and polyaluminium compounds such as polyaluminium chlorides, polyaluminium sulfates, polyaluminium compounds containing both ions, chloride and sulfate, polyaluminium silicate sulfates and mixtures thereof, anionic vinyl addition polymers, and combinations thereof.

The process according to the invention is preferably used in the manufacture of paper from a suspension comprising cellulose fibers and optionally fillers having a high conductivity. The conductivity of the pulp is

Generally at least 0.20 mS / cm, preferably at least 0.5 mS / cm, preferably at least 3.5 mS / cm. Very good sizing results were observed at conductivity levels higher than 5.0 mS / cm or even higher than 7.5 mS / cm. Conductivity can be measured using standard equipment such as the WTW LF 539 from Christian Berner. The above values are preferably determined by measuring the conductivity of the cellulosic suspension that is introduced into or present in the headbox of the paper machine, or alternatively by measuring the conductivity of the white water obtained by dewatering the suspension. A high level of conductivity means a high content of salts (electrolytes), wherein the various salts may be salts of mono-, bivalent and polyvalent cations such as alkali metals, e.g.

On ^T and K, aluminum ions, ions, and mono-, halides, carbonates, alkaline metals such as Al ³⁺ , binary and earth metals, eg 2+, 2 +

Mg ²⁺ , e.g.

Cl ^-, sulfates, e.g.

Ca a

And polyaluminium polyvalent anions such as preferably at least 400 cellulose fibers

SO / a HSO4 ^- ,

CO ₃ ^Z- and HCO3 ^- , silicates and low molecular weight organic acids. The invention is particularly suitable for making paper from pulp having a high salt content of divalent and polyvalent cations, as a rule, the cation content is at least 200 ppm, preferably at least 300 ppm and ppm. Salts may be derived from a filler used for papermaking, particularly in integrated papermaking lines, where a concentrated aqueous suspension of papermaking fibers is normally mixed with water to form a dilute slurry suitable for papermaking in a papermaking line. The salt may also be derived from various additives introduced into the pulp, fresh water fed into the process, or may be added intentionally. Further, the salt content is generally higher in the process where the white water is largely recirculated, which can lead to significant accumulation of salts in the water circulating in the process.

The invention further encompasses methods of making paper, wherein:

white water is largely recirculated, i.e. with a high degree of water circulation closed, using for example 0 to 30 tonnes of fresh water per tonne of dry paper produced, generally less than 20, suitably less than 15, preferably less than 10 and in particular less than 5 tonnes of fresh water per tonne of paper. The recirculation of the white water in the processes suitably comprises mixing the white water with cellulosic fibers and / or optionally fillers to form a suspension to be sized; preferably it comprises mixing the white water with a suspension comprising cellulose fibers and optionally a filler before the suspension enters the sizing screen.

Other additives customary in paper manufacture may be used in combination with the additives of the invention, such as dry strength agents and wet strength agents. The cellulosic suspension may also contain mineral fillers of the conventional type, such as kaolinitic clay, kaolin, titanium dioxide, gypsum, talc and natural and synthetic calcium carbonate, for example chalk, ground limestone and precipitated calcium carbonate.

The process of the invention is used for the production of paper. The term paper, as used herein, includes not only paper and paper manufacture, but also other sheet-like formations such as paperboard and paperboard and their manufacture. The process can be used in the manufacture of paper from various types of cellulose-containing fiber suspensions, and these suspensions should suitably contain at least 25% by weight, preferably at least 50% by weight. of these fibers, based on dry matter. The suspensions may be based on chemical pulp fibers such as kraft, sulphite and organosolv pulps, mechanical pulps such as thermomechanical pulps, chemo-thermo-technical pulps, refined pulp and wood, both hard and soft wood, and may also be based on recycled fibers, optionally from bleached pulp, and mixtures thereof. In particular, the invention is

-30 · · · · · · · · · · · · · 30 30 30 30 30 30 30 30 30 30 30 30 · 99 suitable for making paper from pulp-based suspensions containing recycled fibers and bleached pulp, and the cellulosic fiber content of this origin can be up to 100%, preferably 20 to 100%.

DETAILED DESCRIPTION OF THE INVENTION

The invention is further illustrated by the following examples, but is not limited thereto. Parts and% are always parts and% by weight unless otherwise indicated.

In all examples, the sizing dispersions and the sizing promoter were added separately to the cellulosic suspension. Further, if the promoter contained more than one polymer having an aromatic group, these polymers were added

to the suspension to the dispersion. especially with regard to yourself each other and considering Example 1 The sizing effect of the process was evaluated for. use Cobb test 60. She was ready anionic šlichtovací dispersion containing a dimer alkylketene, condensed

naphthalenesulfonate and dimethylammonium chloride dihydrogenated tall oil. The sizing dispersion had an AKD content of 30% and contained 4% dimethylammonium chloride dihydrogenated tall oil and 6% condensed naphthalene sulfonate based on AKD. The sizing dispersion was added to the stock in an amount of 5 kg AKD / ton dry stock.

Further, cationic starch with a DS 0.065 cationic substitution relative to the nitrogen containing benzyl groups and / or the condensed naphthalenesulfonate (available under the trade name Tamol®) contained in the sizing promoter was added to the stock. In addition, other constituents included in the sizing were added to the pulp

9 · «9,999 · *

-31- 9 · to 9 99 ·····

For example, a cationic starch without aromatic groups having a DS of 0.065 and anionic inorganic silica sol particles.

The pulp used consisted of 80% by weight of bleached birch / pine (60/40) kraft pulp and 20% by weight.

CaCC> 3, refined to 200 CSF and containing 0.3 g / l of Na ₂ SO ₄ pulp having a conductivity of 461 μΞ / cm and a pH of 8.1.

Table 1

Test no. anionic šlichtovací dispersion (kg of sizing agent / ton of dry stock) cationic starch containing aromatic groups (kg / tonne dry stock) cationic starch without aromatic groups (kg / ton dry stock) test 1 0.5 0 10 test 2 0.5 10 0 test 3 0.5 10 0

Test C. Condensed naphthalenesulfonate (kg cond / ton dry stock) anionic silica particles (kg of silica particles / ton of dry stock) Cobb 60 (g / m ² ) test 1 0 1 45.2 test 2 0 1 33.5 test 3 1 0 2 9.3

Example 2

The sizing effect of the process was evaluated (using the Cobb 60 test) using the same anionic sizing dispersion, the same sizing promoter, and the same stock as in Example 1, but calcium chloride was added to the stock to adjust the conductivity to 5000 µε / ατ. The amounts of polymers added in the promoter and sizing agent (AKD) are shown in Table 2.

-32 ··· ····························· · · · · · · · · · · · · · · · · · · · · · ·

Table 2

Test no. anionic šlíchtovací dispersion (kg of sizing agent / ton of dry stock) cationic starch containing aromatic groups (kg / tonne dry stock) cationic starch without aromatic groups (kg / ton dry stock) test 1 0, 5 0 12 test 2 0.5 12 0 test 3 0.5 10 0

Test C. Condensed naphthalenesulfonate (kg cond / ton dry stock) anionic silica particles (kg of silica particles / ton of dry stock) Cobb 60 (g / m ² ) test 1 0 O t — i 75 test 2 0 1.0 28 test 3 1 0 27.8

Example 3

An anionic size dispersion was prepared containing 8.9% commercially available alkyl ketene dimer, 0.89% aromatic-substituted cationic starch having a DS of 0.065 containing benzyl groups, and 0.22% condensed with the Tamol® trade name in amounts of 0.0115% naphthalene sulfonate available under anionic dispersion was added to 0.0140% (dry matter, see table)

3), based on ketene dimer, to a cellulosic suspension (dry matter) containing 30% pine, 30% beech, 40% eucalyptus and 15% precipitated CaCO ₃ . The conductivity of the suspension was 500 pS / cm. A sizing promoter containing benzyl-substituted starch having DS 0.065 and condensed naphthalene sulfonate available under the trade name Tamol® (Test 2) was also added to the suspension. The same anionic dispersion was also added to the same suspension, but the sizing promoter added to the suspension contained no aromatic polymers.

• φ

-33 »· φ Φ

The sizing promoter contained starch with DS 0.065 having aromatic groups and anionic inorganic silica particles as sol (test 1)). The amount of polymer in the promoter and sizing agent (AKD) in the dispersion is shown in Table 3.

Table 3

Test no. anionic šlichtovaci dispersion (kg of sizing agent / ton of dry stock) cationic starch containing aromatic groups (kg / tonne dry stock) cationic starch without aromatic groups (kg / ton dry stock) test 1 0,115 0 5 test 1 0.125 0 5 test 1 0, 140 0 5 test 2 0, 115 5 0 test 2 0.125 5 0 test 2 0, 140 5 0

Test C. Condensed naphthalenesulfonate (kg cond / ton dry stock) anionic silica particles (kg of silica particles / ton of dry stock) Cobb 60 (g / m ² ) test 1 0 0.120 90.0 test 1 0 0, 120 50.0 test 1 0 0.120 29, 0 ' test 2 0.120 0 28.0 test 2 0, 120 0 27.0 test 2 0.120 0 25, 5

Example 4

In this example, the same dispersion, the same promoter, and the same suspension (pulp) were used as in Example 3, except that the conductivity was set to 5000 pS / cm. The amounts of sizing agent and polymers in the promoter are ν · ·

φ 00 · 0 0 * * 0 · 0 · · 0 · · · · · · · · · · · · · · · · · · · · · · · ·

Table 4

Test no. anionic šlichtovací dispersion (kg of sizing agent / ton of dry stock) cationic starch containing aromatic groups (kg / tonne dry stock) cationic starch without aromatic groups (kg / ton dry stock) test 1 0.140 0 5 test 1 0.160 0 5 test 1 0.180 0 5 test 1 0.200 0 5 test 2 0.100 5 0 test 2 0,115 5 0 test 2 0.125 5 0 test 2 0.140 5 0

Test C. Condensed naphthalenesulfonate (kg cond / ton dry stock) anionic silica particles (kg of silica particles / ton of dry stock) Cobb 60 (g / m ² ) test 1 0 0, 120 150 test 1 0 0.120 137 test 1 0 0.120 138 test 1 0 0.120 110 test 2 0.120 0 47 test 2 0.120 0 35 test 2 0.120 0 33 test 2 0.120 0 25

Example 5

The sizing effect of the process was evaluated using a cationic sizing dispersion containing 15% alkyl ketene dimer, 2% cationic starch, and 0.6% AKD based sodium lignosulfonate (sizing agent).

AA

AA AAAA

-35 AAA A A A A A A

A 1 A A <

A A AA

The cationic sizing dispersion was added to the stock in an amount of 0.5 kg of the sizing agent / tonne of dry stock. Polymers included in the sizing promoter (Table 5) included condensed naphthalene sulfonate, cationic starch without aromatic groups having a DS of 0.065, cationic starch containing aromatic groups having a DS of 0.065, and anionic inorganic silica particles in sol form. The amounts of polymers added are apparent from Table 5. The pulp used was the same as in Example 2 and had a pH of 8.1 and a conductivity, adjusted by the addition of calcium chloride, of 5000 μβ / οπι.

Table 5

Test no. cationic šlichtovací dispersion (kg of sizing agent / ton of dry stock) cationic starch containing aromatic groups (kg / tonne dry stock) cationic starch without aromatic groups (kg / ton dry stock) test 1 0.5 0 10 test 2 0.5 0 10 test 3 0, 5 10 0

Test C. Condensed naphthalenesulfonate (kg cond / ton dry stock) anionic silica particles (kg of silica particles / ton of dry stock) Cobb 60 (g / m ² ) test 1 0 1 55 test 2 1 0 34 test 3 1 0 27.8

Example 6

The sizing effect of the process was evaluated using the Cobb 60 test. Anionic sizing dispersions containing alkyl ketene dimer, condensed naphthalene sulfonate and dimethylammonium chloride dihydrogenated ♦ * tititite were prepared.

-36 «« · 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 Tall oil. The sizing dispersion had an AKD content of 30% and contained 4% dimethylammonium chloride dihydrogenated tall oil and 6% condensed naphthalenesulfonate based on AKD. The sizing dispersion was added to the stock in an amount of 0.3 kg AKD / ton dry stock.

The sizing promoter contained a cationic starch with a DS 0.065 cationic substitution having benzyl groups, a non-aromatic starch with a DS 0.065 cationic substitution, condensed naphthalene sulfonate, and melamine sulfonate. The sizing promoters and the amounts added were listed in Table 6.

polymers of the promoter are

The pulp used consisted of birch / pine (60/40) kraft pulp CaCO3, refined to 200 CSF and containing 0.3 providing a conductivity of 555 μΞ / αη and a pH of 8.22.

% wt. % and 20 wt. g / 1 pulp

Table 6

Test no. anionic šlichtovací dispersion (kg of sizing agent / ton of dry stock) cationic starch containing aromatic groups (kg / tonne dry pulp) cationic starch without aromatic groups (kg / ton dry pulp) test 1 0.3 10 test 2 0, 3 10 test 3 0.3 10. - test 4 0.3 10

Test C. Condensed naphthalene sulfonate (kg cond / ton dry pulp) melamine sulphonate (kg of silica particles / tonne dry stock) Cobb 60 (g / m ² ) test 1 1 33 test 2 1 52 test 3 1 35 test 4 1 68

-37 · 404 404 404 404 404 404 404 404

Míarj-w • o ·. A · »» »a a a a a a a a a a a a a a a« «« «« «

Claims (87)

PATENT CLAIMS A method for sizing a paper, comprising adding (i) a sizing dispersion comprising a sizing agent and a polymer having one or more aromatic groups, and (ii) a sizing promoter comprising a polymer having one or more sizing agents to an aqueous suspension containing cellulosic fibers and optionally fillers. % of the aromatic groups, the formed suspension is shaped and dewatered, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. The method according to claim 1, characterized in that the sizing dispersion is anionic or cationic. The method of claim 1, wherein the sizing agent is a cellulose-reactive sizing agent. The method of claim 3, wherein the sizing agent is ketene dimer or acid anhydride. The method of claim 3, wherein the sizing agent is a ketene dimer. The method of claim 1, wherein the polymer having one or more aromatic groups contained in the sizing promoter has an electrical charge. The method of claim 1, wherein the polymer having one or more aromatic groups contained in the sizing promoter is anionic or cationic. ·· ···· «· Φ · • · φ · φ Μ ·· -38 · 9 * φ φ φ φ «r r r r 38 38 38 38 38 A method for sizing a paper, comprising adding (i) a sizing dispersion comprising a sizing agent, a polymer having one or more aromatic groups, and (ii) a sizing promoter comprising a first polymer having one or more; a plurality of aromatic groups and a second polymer having one or more aromatic groups, the formed suspension is shaped and dewatered, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. The method of claim 8, wherein the first and second sizing promoter polymer are added separately to the aqueous suspension. The method of claim 8, wherein the sizing dispersion is anionic or cationic. The method of claim 8, wherein the sizing agent is a cellulose-reactive sizing agent. The method of claim 11, wherein the sizing agent is ketene dimer or acid anhydride. The method of claim 11, wherein the sizing agent is a ketene dimer. 14. The method of the first and second polymer, having an electric charge. A method according to claim 1, characterized in that it is contained in a sizing promoter, claim 8, characterized in that it is contained in a sizing promoter, -39 have opposite charges. A method of sizing a paper, comprising adding (i) a sizing dispersion comprising a sizing agent and a polymer having one or more aromatic groups, and (ii) a sizing promoter comprising a cationic organic polymer having one to a water suspension containing cellulosic fibers and optionally fillers. or more aromatic groups, and an anionic polymer having one group, which is in turn a polysaccharide or natural aromatic polymer, the formed suspension is shaped and dewatered, the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. or more aromatic polymerized polymer The method of claim 16, wherein the sizing dispersion is anionic or cationic. The method of claim 16, wherein the sizing agent is a cellulose-reactive sizing agent. 19. The method of claim 18 wherein the sizing agent is ketene dimer or acid anhydride. 20. The method of claim 18 wherein the sizing agent is a ketene dimer. A process according to claim cationic organic polymer cationic polysaccharide or polymer. 16, characterized in that the sizing promoter is a cationic vinyl addition Method according to claim 16, characterized in that: The -40 cationic organic polymer of the promoter is a cationic polysaccharide. The method of claim 16, wherein the anionic polymer of the promoter is a sequentially polymerized polymer or a natural aromatic polymer. 24. The method of claim 16, wherein the anionic polymer of the promoter is a naphthalene sulfonate condensation polymer or a modified lignin polymer. 25. The method of claim 24, wherein the anionic polymer of the promoter is a naphthalene sulfonate condensation polymer or lignin sulfonate. The method of claim 21, wherein the cationic organic polymer is a cationic polysaccharide having the general structural formula (I): .'Rí, · (O, I X 'p__. _A —N ⁺ —R ₂ ) _n I R ₃ wherein P is a polysaccharide residue; A is a chain comprising C and H atoms, connecting N to the polysaccharide residue, R 1 and R ₂ represent H or a hydrocarbon group, R ₃ is an aromatic hydrocarbon group, n is an integer from 2 to 300 000, and X - is an anionic counterion; or vinyl addition polymers obtained by polymerizing a cationic monomer or blend of monomers comprising a cationic monomer represented by Formula (II) those titi • titi • I «• I • · • · • I ti ti • ti ti (II) x 'CH ₂ = c - r ₂ I: O. O = c - A - B1 - N - Q . Wherein R 1 is H or CH ₃ ; R ₂ and R ₃ are alkyl groups having 1 to 3 carbon atoms, Αχ is O or NH, χ is an alkylene group having 2 to 8 carbon atoms or a hydroxypropylene group, Q is a substituent containing an aromatic group, and X is an anionic counterion. The method of claim 22, wherein the cationic organic polymer is a cationic polysaccharide having the general structural formula (I): Ri (I) I X ‘ P — A — N ⁺ —R ₂ ) _n I. R ₃ wherein P is a polysaccharide residue; A is a chain comprising C and H atoms, connecting N to the polysaccharide residue, R _x and R ₂ represent H or a hydrocarbon group, R ₃ is an aromatic hydrocarbon group, n is an integer of 2 to 300 000, and X "is an anionic counterion. A process according to claim 27, wherein A is an alkylene group having 2 to 18 carbon atoms, optionally interrupted or substituted by one or more heteroatoms, R 1 and R ₂ both represent H or an alkyl group having 1 to 3 carbon atoms; R ₃ is benzyl or phenylethyl. The method of claim 16, wherein the cationic organic polymer and the anionic polymer of the sizing promoter are added to the aqueous suspension. -4230. The method of claim 16, wherein the anionic polymer of the sizing promoter is added to the aqueous suspension after the sizing dispersion and the organic polymer of the sizing promoter. separately. cationic 31. 10. The method of claim 16, wherein: se by that conductivity the suspension is at least 3.5 mS / cm. 32. The method of claim 31, characterized in that: se by that conductivity the suspension is at least 4.5 mS / cm. 33. A method of sizing paper in which se to water groups to which the polysaccharide or or more aromatic polymerized polymer, groups to which the polysaccharide or suspension containing cellulose fibers and optionally fillers are added by (i) a sizing dispersion comprising a sizing agent and the anionic polymer having one or more aromatic is a sequentially polymerized polymer, natural aromatic polymer wherein the amount of sizing dispersion added to the slurry is about 0.01 to about 5.0 wt%, calculated as the sizing agent based on dry fibers; and (ii) a sizing promoter comprising a cationic organic polymer having one or more aromatic groups, and the anionic polymer having one is a naturally occurring aromatic polymer, wherein the amount of cationic polymer added to the suspension is about 0.001 to about 3% by weight based on dry fibers, and the amount of anionic polymer added to the suspension is about 0.001 to about 3% by weight, based on dry fibers; the formed suspension is shaped and dewatered, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. 9. 9 The method of claim 33, wherein the cationic organic polymer is a cationic polysaccharide or a cationic vinyl addition polymer. The method of claim 33, wherein the cationic organic polymer is a cationic polysaccharide. The method of claim 34, wherein the cationic organic polymer is a cationic polysaccharide having the general structural formula (I): R (O). I X '. P - (- A - N ⁺ - R ₂ ) _n I R ₃ ': wherein P is a polysaccharide residue; A is a chain comprising C and H atoms, connecting N to the polysaccharide residue, R 1 and R ₂ represent H or a hydrocarbon group, R ₃ is an aromatic hydrocarbon group, n is an integer from 2 to 300 000, and X is an anionic counterion; or a vinyl addition polymer obtained by polymerizing a cationic monomer or a monomer mixture containing a cationic monomer of the general formula (II) CH ₂ —C - Fh ·. R ₂ (II) · I!,. O = c — A — B! - N —QX •. R ₃ wherein R is H or CH _3; R ₂ and R ₃ are alkyl groups having 1 to 3 carbon atoms, Αχ is O or NH, χ is an alkylene group having 2 to 8 carbon atoms or a hydroxypropylene group, Q is a substituent containing an aromatic group, and X is an anionic counterion. • this -44- • · • · • · · • it to it • this · · · · 37. The method of claim 35, characterized with that cationic organic polymer Yippee cationic polysaccharide having the general structural formula (I): Ri (0 I · X ... p — A — N ⁺ - R ₂ ) nl r ₃ where P is a polysaccharide residue; A is a chain comprising C and H atoms, connecting N to the polysaccharide moiety, R 1 and R ₂ represent H or a hydrocarbon group, R 3 is an aromatic hydrocarbon group, n is an integer from 2 to 300 000, and X ^- is an anionic counterion. 38. The process of claim 37 wherein A is C2-C18 alkylene optionally interrupted or substituted with one or more heteroatoms; R 1 and R _{2 are} both H or an alkyl group having 1 to 3 carbon atoms; R 3 is benzyl or phenylethyl. 39. The method of claim 33 wherein the anionic polymer of the sizing dispersion and the promoter is a sequentially polymerized polymer or a natural aromatic polymer. · 40. The method of claim 39, wherein the anionic polymer is a naphthalene sulfonate condensation polymer, a polystyrene sulfonate polymer, or a modified lignin polymer. 41. The method of claim 39, wherein the anionic polymer is a naphthalene sulfonate condensation polymer or a modified lignin polymer. • · 42. The method of claim 39, wherein the anionic polymer is a naphthalene sulfonate condensation polymer or lignin sulfonate. 43. The method of claim 33, wherein the cationic organic polymer and the anionic polymer of the sizing promoter are added separately to the aqueous suspension. The method of claim 33, wherein the anionic polymer of the sizing promoter comprises an aqueous suspension after the sizing dispersion and an organic polymer of the sizing promoter. is by adding to the cationic 45. Way according to Claim 33 characterized se by that conductivity suspension is at least 3.5 mS / cm. 46. Way according to Claim 45 characterized se by that conductivity suspension is at least 4.5 mS / cm. 47. Way according to Claim 33 characterized se by that the sizing agent is a cellulose-reactive sizing agent. 48. A method of sizing paper comprising adding (i) a sizing dispersion comprising a sizing agent, a cationic organic polymer having one or more aromatic groups, and an anionic polymer having one or more aromatic groups to an aqueous slurry containing cellulosic fibers and optionally fillers; is a sequentially polymerized polymer, polysaccharide or natural aromatic polymer, the amount of sizing dispersion added to the slurry being about 0.01 to about 5.0 wt%, calculated as the sizing agent based on dry fibers; and (ii) a sizing promoter comprising a cationic organic polymer having one or more anionic polymer having one group of polysaccharide or aromatic groups, and or more aromatic polymerized polymer, is a sequential natural aromatic polymer, wherein the amount of cationic polymer added to the suspension is about 0.001 to about about 3 wt.%, based on dry fibers, and the amount of anionic polymer added to the suspension is about 0.001 to about 3 wt.%, based on dry fibers; the formed suspension is shaped and dewatered, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. 49. The method of claim 48, wherein the cationic organic polymer of the sizing dispersion and the promoter is a cationic polysaccharide or a cationic vinyl addition polymer. 50. The method of claim 48, wherein the cationic organic polymer of the sizing dispersion and the promoter is a cationic polysaccharide. The method of claim 49, wherein the cationic organic polymer is a cationic polysaccharide having the general structural formula (I): Ri (I) I, X ' P- ~ (-A-N '- _{R2) n} I r ₃ - ·· where P is a polysaccharide residue; A is a chain comprising C and H atoms, connecting N to the polysaccharide residue, R 1 and R ₂ represent H or a hydrocarbon group, R 3 is an aromatic hydrocarbon group, n is an integer from 2 to 300 000, and X "is ·· ···· anionic protion; or a vinyl addition polymer obtained by polymerizing a cationic monomer or a monomer mixture containing a cationic monomer of the general formula (II) CH ₂ = C — R x R ₂ : ···., (IL) 1 li - :, · ,,, ',, O = C - Αχ - Βχ - N - Q. X wherein R 1 is H or CH 3; R ₂ and R ₃ are alkyl groups having 1 to 3 carbon atoms, Αχ is 0 or NH, χ is an alkylene group having 2 to 8 carbon atoms or a hydroxypropylene group, Q is a substituent containing an aromatic group, and X "is an anionic counterion. The method of claim 50, wherein the cationic organic polymer is a cationic polysaccharide having the general structural formula (I): R1 (Ó IX 'p __ (A A — N ⁺ —R ₂ ) _n I,. - / .. 1 year ₃ . ,. wherein P is a polysaccharide residue; A is a chain comprising C and H atoms, connecting N to the polysaccharide residue, R x and R ₂ represent H or a hydrocarbon group, R ₃ is an aromatic hydrocarbon group, n is an integer of 2 to 300 000, and X 1 is an anionic counterion. 53. The process of claim 52 wherein A is C2-C18 alkylene optionally interrupted or substituted with one or more heteroatoms; R x and R ₂ both represent H or an alkyl group having 1 to 1 -48 »4 ·« ·· ·· ·· 3 carbon atoms; R ₃ is benzyl or phenylethyl. 54. The method of claim 48, wherein the anionic polymer of the sizing dispersion and the promoter is a sequentially polymerized polymer or a natural aromatic polymer. 55. The method of claim 54 wherein the anionic polymer is a naphthalene sulfonate condensation polymer, a polystyrene sulfonate polymer, or a modified lignin polymer. 56. The method of claim 54 wherein the anionic polymer is a naphthalene sulfonate condensation polymer or a modified lignin polymer. . . 57. The process of claim 54 wherein the anionic polymer is a naphthalene sulfonate condensation polymer or lignin sulfonate. 58. The method of claim 48, wherein the cationic organic polymer and the anionic polymer of the sizing promoter are added separately to the aqueous suspension. 59. The method of claim 48, wherein the anionic polymer of the sizing promoter is added to the aqueous suspension after the sizing dispersion and the cationic organic polymer of the sizing promoter. 60. The method of claim 48, wherein the conductivity of the suspension is at least 3.5 mS / cm. 61. The method of claim 60 wherein the conductivity of the suspension is at least 4.5 mS / cm. ·· ···· 62. The method of claim 48, wherein the sizing agent is a cellulose-reactive sizing agent. 63. A method of sizing paper comprising adding (i) a sizing dispersion comprising a sizing agent and an anionic polymer having one or more aromatic groups which is a naphthalene sulfonate condensation polymer, a polystyrene sulfonate polymer, or a modified anionic polymer to an aqueous suspension containing cellulosic fibers and optionally fillers. a lignin polymer, wherein the amount of sizing dispersion added to the slurry is about 0.01 to about 5.0% by weight, calculated as the sizing agent based on dry fibers; and (ii) a sizing promoter comprising a cationic organic polymer having one or more aromatic groups which is a cationic polysaccharide and an anionic polymer having one or more aromatic groups which is a naphthalene sulfonate condensation polymer or modified lignin polymer, wherein the amount of cationic polymer added to the suspension is about 0.001 to about 3% by weight, based on dry fibers, and the amount of anionic polymer added to the suspension is about 0.001 to about 3% by weight, based on dry fibers; the formed suspension is shaped and dewatered, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. The method of claim 63, wherein the cationic organic polymer is a cationic polysaccharide having the general structural formula (I): fcfc fcfc ·· - 50 ································ Rt O) i X ' P - (- A - N ^{+ -} R ₂ ) _n ^R 3 wherein P is a polysaccharide residue; A is a chain comprising C and H atoms, connecting N to the polysaccharide moiety, R 1 and R 2 represent H or a hydrocarbon group, R 3 is an aromatic hydrocarbon group, n is an integer from 2 to 300 000, and X is an anionic counterion. 65. The process of claim 64 wherein A is C2-C18 alkylene optionally interrupted or substituted with one or more heteroatoms; R ₁ and R ₂ both represent H or an alkyl group having 1 to 3 carbon atoms; R 3 is benzyl or phenylethyl. 66. The method of claim 63 wherein the anionic polymer of the sizing dispersion and the promoter is a naphthalene sulfonate condensation polymer or a modified lignin polymer. 67. The method of claim 66, wherein the anionic polymer is a naphthalene sulfonate condensation polymer or lignin sulfonate. 68. The method of claim 63 wherein the cationic organic polymer and the anionic polymer of the sizing promoter are added separately to the aqueous suspension. 69. The method of claim 63, wherein the anionic polymer of the sizing promoter comprises an aqueous suspension after the sizing dispersion and an organic polymer of the sizing promoter. is by adding to the cationic 9 «999 · 98 9 9 «·· 9 9 ·· »999 * 9 999 99 99 9 · -51 - 9 < 9 9 9 9 9 9 9 9 9 9 99 9 · 70. The method of claim 63, characterized se by that conductivity the suspension is at least 3.5 mS / cm. 71 The method of claim 63, characterized se by that conductivity the suspension is at least 4.5 mS / cm. 72. The method of claim 63, characterized se by that the sizing agent is a cellulose-reactive sizing agent. 73. A method of sizing paper comprising adding (i) a sizing dispersion comprising a sizing agent, a cationic organic polymer having one or more aromatic groups which is a cationic polysaccharide, and an anionic polymer having one to an aqueous suspension containing cellulosic fibers and optionally fillers. or more aromatic groups which are naphthalene sulfonate condensation polymer, polystyrene sulfonate polymer or modified lignin polymer, wherein the amount of sizing dispersion added to the slurry is about 0.01 to about 5.0 wt%, calculated as the dry agent sizing agent; and (ii) a sizing promoter comprising a cationic organic polymer having one or more aromatic groups which is a cationic polysaccharide and an anionic polymer having one or more aromatic groups which is a naphthalene sulfonate condensation polymer, polystyrene sulfonate polymer or modified lignin polymer, wherein the amount of cationic polymer added to the suspension is about 0.001 to about 3% by weight based on dry fibers, and the amount of anionic polymer added to the suspension is about 0.001 to about 3% by weight based on dry fibers; the formed suspension is shaped and dewatered, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. • * 74. The method of claim 73, wherein the cationic organic polymer is a cationic polysaccharide having the general structural formula (I): «(I) I X P - (- A - N ⁺ - R ₂ ) _n . ir ₃ wherein P is a polysaccharide residue; A is a chain containing C and H atoms, connecting N to the polysaccharide residue, R 1 and R ₂ represent H or a hydrocarbon group, R 3 is an aromatic hydrocarbon group, n is an integer from 2 to 300 000, and X is an anionic counterion. 75. The method of claim 74 wherein A is C2-C18 alkylene optionally interrupted or substituted with one or more heteroatoms; R 1 and R _{2 are} both H or an alkyl group having 1 to 3 carbon atoms; R 3 is benzyl or phenylethyl. 76. The method of claim 73, wherein the anionic polymer of the sizing dispersion and the promoter is a naphthalene sulfonate condensation polymer or a modified lignin polymer. 77. The method of claim 76, wherein the anionic polymer is a naphthalene sulfonate condensation polymer or lignin sulfonate. 78. The method of claim 73, wherein the cationic organic polymer and the anionic polymer of the sizing promoter are added separately to the aqueous suspension. «• • • • • • φ φ φ φ • · -53 · «· Φ · φ φ · φφφ · · φ φ φ φ φ φφ φφ 79. The method of claim 73, wherein the anionic polymer of the sizing promoter is added to the aqueous suspension after the sizing dispersion and the cationic organic polymer of the sizing promoter. 80. Way according to claim 73, characterized by that conductivity suspension is at least 4, 5 mS / cm. 81 Way according to claim 73, characterized by that the sizing agent is a cellulose-reactive sizing agent. 82. A method of sizing a paper comprising adding (i) a sizing dispersion comprising a sizing agent and an anionic polymer having one or more aromatic groups which is a naphthalene sulfonate condensation polymer, a polystyrene sulfonate polymer, or a modified lignin to an aqueous suspension containing cellulosic fibers and optionally fillers. a polymer, wherein the amount of sizing dispersion added to the slurry is about 0.01 to about 5.0% by weight, calculated as the sizing agent based on dry fibers; and (ii) a sizing promoter comprising a cationic organic polymer having one or more aromatic groups which is a cationic polysaccharide having the general structural formula (I): Ri (I) .1 X ' P - (- A - N ⁺ - R ₂ ) _n I R ₃ wherein P is a polysaccharide residue; A is a chain containing C and H atoms, connecting N to the polysaccharide residue, R _x and R ₂ represent H or a hydrocarbon group, R ₃ is aromatic · «** 0 4 0 0 3 · 4 4 44 4 4 4 4 4 44 44 44 a hydrocarbon group, n is an integer of 2 to 300,000, and X 'is an anionic counterion, and an anionic polymer having one or more aromatic groups, which is a naphthalene sulfonate condensation polymer or modified lignin polymer, the amount of cationic polymer added to the suspension is about 0.001 to about 3% by weight, based on dry fibers, and the amount of anionic polymer added to the suspension is about 0.001 to about 3% by weight, based on dry fibers; the formed suspension is shaped and dewatered, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. 83. The method of claim 82, wherein the anionic polymer of the sizing dispersion and the promoter is a naphthalene sulfonate condensation polymer or a modified lignin polymer. 84. The method of claim 83 wherein the anionic polymer is a naphthalene sulfonate condensation polymer or lignin sulfonate. 85. The process of claim 82 wherein the cationic organic polymer and the anionic polymer of the sizing promoter are added separately to the aqueous suspension. 86. The method of claim 82, wherein the anionic polymer of the sizing promoter comprises an aqueous suspension after the sizing dispersion and an organic polymer of the sizing promoter. is by adding to the cationic 87. The method of claim 82, wherein the conductivity of the suspension is at least 3.5 mS / cm. Α · AAAA -55 tt · · · A A A A A A A A A A A A A A A A AA 88. The method of claim 82, wherein the sizing agent is a cellulose-reactive sizing agent. 89. The method of claim 82 wherein the sizing agent is present in the dispersion in an amount of about 0.1 to about 50% by weight based on the total amount of emulsion. 90. The process of claim 82 wherein the anionic polymer of the sizing dispersion is present in an amount of about 0.1 to about 15% by weight based on the total amount of the sizing agent. 91. A method of sizing a paper, comprising adding (i) a sizing dispersion comprising a sizing agent, a cationic polymer having one or more aromatic groups, which is a cationic polysaccharide having the general structural formula (I) to an aqueous suspension containing cellulosic fibers and optionally fillers. : Ri (I) I X ' P - (- A - N ⁺ - R ₂ ) _n I. R ₃ wherein P is a polysaccharide residue; A is a chain comprising C and H atoms, connecting N to the polysaccharide residue, R 1 and R ₂ represent H or a hydrocarbon group, R ₃ is an aromatic hydrocarbon group, n is an integer of 2 to 300 000, and X is an anionic counterion, and anionic polymer having one or more aromatic groups which is a naphthalene sulfonate condensation polymer, a polystyrene sulfonate polymer or a modified lignin polymer, wherein the amount of sizing dispersion added is Φ Φ φφφφ -56 ΦΦ φ φ φ φ φ φ φ φ φ φ φ φ φ φ • • • • φ φ φ φ • φ φ φ φ φ φ φ φ φ k k k k dry fibers; and (ii) a sizing promoter comprising a cationic organic polymer having one or more aromatic groups which is a cationic polysaccharide having the general structural formula (I): . R? (0 ^X ~ P - (- A - N ^{+ -} R ₂ ) n • I. in . R ₃ wherein P is a polysaccharide residue; A is a chain comprising C and H atoms, connecting N to the polysaccharide residue, R 1 and R ₂ represent H or a hydrocarbon group, R ₃ is an aromatic hydrocarbon group, n is an integer of 2 to 300 000, and X "is an anionic protion, and anionic a polymer having one or more aromatic groups which is a naphthalene sulfonate condensation polymer or a modified lignin polymer, wherein the amount of cationic polymer added to the suspension is about 0.001 to about 3% by weight based on dry fibers, and the amount of anionic polymer added to the suspension is about 0.001 to about 3% by weight, based on dry fibers; the formed suspension is shaped and dewatered, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. 92. The method of claim 91, wherein the anionic polymer of the sizing dispersion and the promoter is a naphthalene sulfonate condensation polymer or a modified lignin polymer. 93. The method of claim 91 wherein the anionic polymer is a naphthalene sulfonate condensation polymer. -57, characterized by an anionic aqueous suspension 4 · • 4 4 4 44 · 4 44 4 4 4 4 4 4 44 4 4 4 4 4 4 4 4 44 44 4 4 4 4 4 4 <45 4 4 4 4 4 44 or lignin sulfonate. The method of claim 91 the cationic organic polymer of the sizing promoter is separated. 95. The method of claim 91, wherein the anionic polymer of the sizing promoter comprises an aqueous suspension after the sizing dispersion and an organic polymer of the sizing promoter. in that the polymer is added by cationic addition 96. The method of claim 91, wherein the suspension conductivity is at least 3.5 mS / cm. 97. The method of claim 91, wherein the sizing agent is a cellulose-reactive sizing agent. 98. The method of claim 91, wherein the sizing agent is present in the dispersion in an amount of about 0.1 to about 50% by weight based on the total amount of the emulsion. 99. The method of claim 91 wherein the anionic polymer of the sizing dispersion is present in an amount of about 0.1 to about 15% by weight based on the total amount of the sizing agent. 100. The process of claim 91 wherein the cationic polymer of the sizing dispersion is present in an amount of about 0.1 to about 15% by weight based on the total amount of the sizing agent.