KR20030042444A - Process for sizing paper - Google Patents

Abstract

The present invention refers to a process for sizing paper which comprises adding to an aqueous suspension containing cellulosic fibres, and optional fillers, (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 aromatic groups, forming and draining the obtained suspension, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.

Description

Paper Sizing Method {PROCESS FOR SIZING PAPER}

Sizing agents Aqueous dispersions or emulsions are used to provide paper and cardboard with improved resistance to penetration and wetting by various liquids in the papermaking process. Sizing agent dispersions are usually added to aqueous suspensions containing cellulose fibers, fillers and various additives. The aqueous suspension is introduced into a headbox which releases the suspension on the wire to form a wet paper web. Microparticles and starch are added to the suspension to promote the dehydration of the suspension on the wire. White water discharged from the wire is usually partially recycled to the papermaking process. Cellulose suspensions contain fillers, sizing agents, charged polymers and a variety of charged contaminants, ie non-fibrous materials such as anionic traces, electrolytes, colloidal materials. Non-fibrous materials affect the sizing efficiency, resulting in poor sizing performance. Large amounts of charged contaminants, such as high amounts of salts in the suspension, make the suspension sizing difficult, making it difficult to obtain species with satisfactory sizing properties. Other compounds in suspensions that reduce sizing are various lipophilic wood extracts from recycled fibers and high yield pulp, ie mechanical pulp. Increasing the amount of sizing agent improves sizing but accumulates sizing agent in white water and increases cost. The accumulation of non-fibrous materials and other components present in the suspension is even more severe in plants where only a small amount of fresh water is introduced into the papermaking process and the white water is excessively recycled. It is therefore an object of the present invention to further improve sizing. Another object of the present invention is to improve sizing when applying sizing agents to cellulose suspensions having high conductivity and high content of lipophilic wood extracts.

WO 99/55964 is added to suspensions in which the drainage and retention aids comprise cationic or amphoteric polysaccharides having hydrophobic groups. Polysaccharides can be used in combination with anionic microparticles and sizing agents.

WO 99/55965 relates to a papermaking method in which drainage and retention aids are added to a suspension comprising a cationic organic polymer having an aromatic group. Cationic organic polymers are used in combination with anionic microparticles.

US 6001166 relates to aqueous alkyl diketone dispersions containing anionic dispersants such as cationic starch and lignin sulfonic acid, condensation of naphthalenesulfonic acid with formaldehyde.

WO9833979 discloses an aqueous dispersion of cellulose reactive sizing agents comprising cationic organic compounds and anionic stabilizers.

The present invention comprises the steps of adding a sizing dispersion comprising a polymer having at least one aromatic group and a sizing agent, a sizing accelerator comprising a polymer having at least one aromatic group to a suspension containing cellulose fibers and fillers, and forming and dehydrating the suspension on a wire. A paper sizing method comprising a sizing dispersion and a sizing promoter are separately added to an aqueous suspension.

It has been found that the invention according to the claims improves the sizing of cellulose fiber-containing aqueous suspensions of high conductivity. In particular, the present invention relates to a sizing agent aqueous dispersion comprising a condensation product of starch with an aromatic group containing less than 95% by weight amylopectin and an aromatic sulfonic acid and an aldehyde. Adding a sizing dispersion comprising a polymer having at least one aromatic group and a sizing agent, a sizing promoter comprising a polymer having at least one aromatic group, to the suspension containing cellulose fibers and fillers, and shaping and dehydrating the suspension on a wire; Related to the paper sizing method, the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.

The sizing agents included in the dispersions of the process of the present invention and added to the suspension include rosin, such as rosin, waxes, fatty acids and resin acid derivatives, for example fortified or esterified, such as fatty amides and fatty esters, such as glycerol triesters of fatty acids. Sizing agents such as cellulose non-reactants or cellulose reactants. Cellulose reactive sizing agents are preferred. The cellulose reactive sizing agent included in the sizing dispersion is selected from cellulose reactants known in the art. Sizing agents are hydrophobic ketene dimers, ketene multimers, acid anhydrides, organic isocyanates, carbamoyl chlorides, in particular ketene dimers and anhydrides, even more ketene dimers. Suitable ketene dimers have the formula (1) and R ¹ and R ² are saturated or unsaturated, usually saturated hydrocarbons and hydrocarbon groups have 8-36 carbons, and usually straight or 12-12 carbons such as hexadecyl and octadecyl groups It is a branched alkyl group. The ketene dimer is liquid at ambient temperature, ie 25 ° C., usually 20 ° C. Suitable acid anhydrides are characterized by formula (2) and R ³ and R ⁴ are the same or different and are saturated or unsaturated hydrocarbon groups having 8-30 carbons or R ³ and R ⁴ are 5-6 hexa ring with -COC- moiety. And may be substituted with a hydrocarbon group containing up to 30 carbons. Commercially used anhydrides include alkyl and alkenyl succinic anhydrides, in particular isooctadecenyl succinic anhydride.

Suitable ketene dimers, anhydrous acids and organic isocyanates include compounds disclosed in US Pat. No. 4,522,686. Suitable carbamoyl chlorides include the compounds disclosed in US Pat. No. 3,887,427.

The sizing dispersion added to the suspension has a sizing agent content of 0.1-50% by weight, in particular 20% by weight or more of the total dispersion / emulsion. Dispersions comprising ketene dimer sizing agents have a ketene dimer content of 5-50% by weight, in particular 10-35% by weight of the total dispersion. Dispersions comprising anhydrous acid sizing agents have an anhydrous acid content of 0.1-30% by weight, in particular 1-20% by weight of the total dispersion. Dispersions containing non-cellulose reactive sizing agents have a sizing agent content of 5-50% by weight, in particular 10-35% by weight. Anionic and cationic polymers included in the sizing dispersion and containing one or more aromatic groups are present in amounts of 0.1-15% by weight of the sizing agent.

The amount of sizing agent added to the aqueous suspension containing cellulose fibers is 0.01-5% by weight, in particular 0.05-1.0% by weight, of the dry weight of cellulose fiber and filler and the dosage is the quality, sizing agent and sizing level of the paper or pulp to be sized. Depends on

Sizing dispersions including polymers containing one or more aromatic groups are anionic or cationic. That is, a dispersant / stabilizer called dispersion system present in the dispersion has an anionic or cationic total charge. Dispersion systems may include dispersants / stabilizers that promote the formation of dispersions or emulsions, such as polyvalent electrolytes, surfactants, and electrolytes. Anionic aqueous sizing dispersions include cationic polyvalent electrolytes (cationic or amphoteric polyelectrolytes with positive total charge) or cationic surfactants and other compounds known in the art if the total charge of the dispersion system is anionic. On the other hand, cationic aqueous sizing dispersions may be used in the field of anionic polyvalent electrolytes (anionic or amphoteric polyelectrolytes with negative total charges) or anionic surfactants and if the total charge of the dispersion system is cationic. Other compounds known in the art.

According to the invention, a suspension containing cellulose fibers and fillers is added to a sizing dispersion comprising a polymer having at least one aromatic group and a sizing agent, a sizing accelerator comprising a polymer having at least one aromatic group, and the suspension is molded and dehydrated on a wire. A paper sizing method comprising the steps is provided wherein the sizing dispersion and the sizing promoter are separately added to the aqueous suspension. Polymers having one or more aromatic groups are non-charged or charged, in particular charged. The polymer is cationic, amphoteric or anionic. Suitable polymers are derived from natural sources such as starch, guar gum, cellulose, chitin, chitosan, glycan, galactan, glucan, xan gum, pectin, mannan, polysaccharides such as dextrins, and starch and guar gum. Preferred, starch is potato, corn, wheat, tapioca, rice, waxy corn, barley and vinyl addition polymers (chain-like polymers) such as acrylate, acrylamide and vinyl amide based polymers, step- like polyurethane Growth polymers. Organic polymers selected from polysaccharides, vinyl addition polymers such as starch and acrylamide based polymers are suitable.

The aromatic group of the polymer may be present in the polymer backbone or the aromatic group may be an accessory group attached or extended to the polymer backbone or as an accessory group attached or extended to the polymer backbone (backbone).

Sizing promoters include additional polymers having one or more aromatic groups. The total charge of the two polymers containing at least one aromatic group included in the sizing promoter has a counter charge and is added separately to the aqueous suspension. If the polymer does not contain melamine or melamine derivatives, the polymer included in the sizing promoter has an aromatic group.

According to the invention a sizing dispersion comprising a polymer having at least one aromatic group and a sizing promoter comprising a first polymer having at least one aromatic group and a second polymer having at least one aromatic group are added separately to the aqueous suspension. Addition separately means that the sizing dispersion and the sizing promoter are added to the cellulose suspension (diluted stock) at different points or at the same point but with time differences. In addition, if the sizing promoter consists of two polymers having aromatic groups, they are also preferably added separately.

In one aspect the invention relates to a polymer comprising at least one aromatic group and a sizing agent in a suspension containing cellulose fibers and fillers, at least one aromatic group being a cationic organic polymer having at least one aromatic group and a sizing dispersion comprising at least one aromatic group. Adding a sizing promoter, including a polymer having a group, wherein the polymer of the sizing dispersion is a cationic organic polymer having at least one aromatic group or an anionic organic polymer having at least one aromatic group, wherein the anionic polymer is a condensation polymer, a polysaccharide or a natural aromatic Polymers, especially condensation polymers, polysaccharides, cationic polymers are cationic polysaccharides or cationic vinyl addition polymers, and anionic polymers are naphthalene sulfonate condensation polymers, polystyrene sulfonate poly Or a modified lignin sulfonate, related to the paper sizing method which comprises forming and dewatering the suspension on a wire, and a sizing dispersion and a sizing promoter is separately added to the aqueous suspension.

In another aspect, the paper sizing process comprises a sizing dispersion comprising a sizing agent, a cationic organic polymer having at least one aromatic group or an anionic polymer having at least one aromatic group, and a cation having at least one aromatic group in a suspension containing cellulose fibers and fillers. Adding a sizing promoter comprising an organic polymer and an anionic polymer having at least one aromatic group selected from condensation polymers, polysaccharides and natural aromatic polymers, the anionic polymer of the sizing dispersion is a condensation polymer or a natural aromatic polymer, and wire the suspension It relates to a paper sizing method comprising the step of forming and dehydrating a bed, wherein the sizing dispersion and the sizing promoter are separately added to the aqueous suspension.

In another aspect, the paper sizing process comprises a sizing dispersion comprising at least one aromatic group and an anionic polymer having at least one aromatic group selected from sizing agents and condensation polymers, polysaccharides and natural aromatic polymers in a suspension containing cellulose fibers and fillers. Cationic organic polymers, in particular cationic polysaccharides or cationic vinyl addition polymers (preferably cationic polysaccharides) and anionic polymers having at least one aromatic group selected from condensation polymers, polysaccharides and natural aromatic polymers. The sizing promoter included was added, and the amount of sizing dispersion was 0.01-5.0 wt% as calculated by the sizing agent for the dry fibers and the amount of cationic polymer added to the suspension was 0.001-3 wt% as calculated by the sizing agent for the dry fibers and Added anions The amount of the polymer is 0.001-3% by weight, calculated as a sizing agent for dry fibers, relates to a paper sizing method comprising the step of forming and dehydrating the suspension on a wire, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. .

In another aspect, the paper sizing process is cationic with one or more aromatic groups such as sizing agents, cationic polysaccharides or cationic vinyl addition polymers (preferably cationic polysaccharides) in suspensions containing cellulose fibers and fillers. Cationic organic polymers having at least one aromatic group and sizing dispersions including polymers and anionic polymers having at least one aromatic group selected from condensation polymers, polysaccharides and natural aromatic polymers, in particular cationic polysaccharides or cationic vinyl addition polymerizations Adding a sizing accelerator comprising a polymer (preferably a cationic polysaccharide) and an anionic polymer having at least one aromatic group selected from condensation polymers, polysaccharides and natural aromatic polymers, the amount of sizing dispersion being dependent on the dry fiber The amount of cationic polymer added to the suspension is 0.01-5.0% by weight, and the amount of cationic polymer added to the suspension is 0.001-3% by weight, and the amount of the anionic polymer added to the suspension is 0.001, -3% by weight, which relates to a paper sizing method comprising forming and dehydrating the suspension on a wire, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.

In another aspect, the paper sizing process comprises at least one aromatic group selected from sizing agents such as cellulose reactive sizing agents, cationic organic polymers having aromatic groups or condensation polymers, polysaccharides and natural aromatic polymers in suspensions containing cellulose fibers and fillers. Anions having aromatic groups selected from condensation polymers, polysaccharides and natural aromatic polymers obtained by polymerizing a sizing dispersion including an anionic polymer having a polymer and a cationic polysaccharide of formula (3) or a cationic monomer of formula (4) Adding a sizing promoter comprising the polymeric polymer.

Wherein P is a residue of the polysaccharide, A is an atom chain containing C and H atoms as a group to attach N to the polysaccharide residue, R ₁ and R ₂ are H or a hydrocarbon group, and R ₃ is an aromatic hydrocarbon Group, n is 2-300,000, X ⁻ is an anionic counter ion,

Wherein R ₁ is H or CH ₃ , R ₂ and R ₃ are alkyl groups having 1-3 carbon atoms, A ₁ is O or NH, B ₁ is alkylene or hydroxy propylene having 2-8 carbon atoms Group, Q is an aromatic group containing substituent, and X ⁻ is an anionic counter ion.

In another aspect, the paper sizing process comprises a sizing agent, such as a cellulose reactive sizing agent, a cationic organic polymer or condensation polymer, a polysaccharide and a natural aromatic polymer (especially polysaccharide and Sizing dispersions comprising anionic polymers having at least one aromatic group selected from natural aromatic polymers) and sizings comprising anionic polymers having aromatic groups selected from condensation polymers, polysaccharides and natural aromatic polymers of formula (3) Adding a promoter, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.

Wherein P is a residue of the polysaccharide, A is an atom chain containing C and H atoms as a group to attach N to the polysaccharide residue, R ₁ and R ₂ are H or a hydrocarbon group, and R ₃ is an aromatic hydrocarbon Group, n is 2-300,000 and X ⁻ is an anionic counter ion.

In another aspect, the paper sizing process comprises at least one selected from sizing agents such as cellulose reactive sizing agents, cationic organic polymers or condensation polymers, polysaccharides and natural aromatic polymers with at least one aromatic group in a suspension containing cellulose fibers and fillers. A sizing dispersion comprising an anionic polymer having an aromatic group and a cationic vinyl addition polymer obtained by polymerizing a cationic monomer of formula (4) and an anionic polymer having an aromatic group selected from a condensation polymer, a polysaccharide and a natural aromatic polymer. Adding a sizing promoter, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension.

Wherein R ₁ is H or CH ₃ , R ₂ and R ₃ are alkyl groups having 1-3 carbon atoms, A ₁ is O or NH, B ₁ is alkylene or hydroxy propylene having 2-8 carbon atoms Group, Q is an aromatic group containing substituent, and X ⁻ is an anionic counter ion.

Anionic polymers (including in accelerators or dispersions, especially accelerators) having one or more aromatic groups are selected from condensation polymers, polysaccharides and natural aromatic polymers unless the anionic polymer is a melamine sulfonic acid condensation polymer. Anionic polymers are usually selected from naphthalene sulfonate condensation polymers such as condensed naphthalene sulfonates, polystyrene sulfonate polymers and modified lignin sulfonates (eg, sulfonate lignin).

According to the invention the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. Although the sizing dispersion may comprise the same polymer as the polymer included in the sizing promoter, an improvement is only observed when the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. Separate addition means that the sizing dispersion and the sizing accelerator, which may comprise a polymer of sizing promoter, are added at different points in the paper mill or at different times at the same point. Cationic organic polymers and anionic polymers that form sizing accelerators are also preferably added separately. Anionic polymers having aromatic groups included in the sizing promoter are added after the sizing dispersion and the cationic organic polymer.

Cationic polymer

Cationic organic polymers having one or more aromatic groups of sizing promoters that may be included in the sizing dispersion are derived from natural or synthetic sources and may be in straight, branched and crosslinked form. Suitable cationic polymers are cationic polysaccharides such as starch, guar gum, cellulose, chitin, chitosan, glycan, galactan, glucan, xan gum, pectin, mannan, dextrin, with starch and guar gum being preferred and , Starch is potato, corn, wheat, tapioca, rice, waxy corn, barley and cationic vinyl addition polymers (cationic chain-growth polymers), cationic polyurethanes such as acrylate, acrylamide and vinylamide based polymers Cationic synthetic organic polymers such as cationic condensation polymers. Preference is given to polysaccharides, ie cationic organic polymers selected from cationic vinyl addition polymers such as starch, acrylamide based polymers having aromatic groups.

The aromatic groups of the cationic organic polymer may be present in the polymer backbone or substituents attached to the backbone. Examples of suitable aromatic groups include aryl, alkaryl and aralkyl groups such as phenyl, phenylene, naphthyl, xylene, benzyl and phenylethyl, in particular benzyl; Cationic groups, including nitrogen-containing aromatic (aryl) groups and derivatives thereof, such as pyridinium and quinolinium, and which may be present in cationic polymers and monomers used to prepare them, may be quaternary ammonium, tertiary amino and acid addition salts thereof. Include.

In one aspect the cationic organic polymer having an aromatic group is selected from cationic polysaccharides. Aromatic groups of polysaccharides may be attached to heteroatoms such as nitrogen or oxygen, and in the case of nitrogen, the heteroatoms are charged. Aromatic groups can be attached to hetero atom containing groups such as amides, esters or ethers, which can be attached to the polysaccharide backbone via the atomic chain. Examples of suitable aromatic groups include aryl and aralkyl groups such as phenyl, phenylene, naphthyl, xylene, benzyl and phenylethyl; Nitrogen-containing aromatic (aryl) groups such as pyridinium and quinolinium and derivatives thereof, wherein at least one substituent attached to the aromatic group has hydroxy, halide (e.g. chloride), nitro, and 1-4 carbon atoms Selected from hydrocarbon groups.

The cationic organic polymer is selected from cationic polysaccharides of formula (3).

Wherein P is a residue of the polysaccharide, A is a group that attaches N to the polysaccharide residue, and is an atomic chain comprising O or N atoms auxiliary to C and H atoms, optionally one or more hetero atoms such as O or N The alkylene group substituted by is usually an alkyleneoxy group or a hydroxy propylene group (-CH ₂ -CH (OH) -CH _2- ), and R ₁ and R ₂ are H, 1-3, in particular one A hydrocarbon group having two carbon atoms, in particular an alkyl group, R ₃ is an aromatic hydrocarbon group including an aralkyl group such as benzyl and phenylethyl groups, n is 2-300,000, especially 5-200,000, even 6-125,000, or R ₁ , R ₂ and R ₃ together with N form an aromatic group containing 5-12 carbon atoms, and X ⁻ is a halide such as an anionic counter ion, in particular chloride.

Cationic polysaccharides modified with aromatic groups can have a wide range of degrees of substitution and cationic degree of substitution (DS _C ) is 0.01-0.5, in particular 0.02-0.3, even 0.025-0.2 and aromatic degree of substitution (DS _H ) 0.01-0.5, in particular 0.02-0.3, even more 0.025-0.2 and anionic degree of substitution (DS _A ) is 0-0.2, in particular 0-0.1, even more 0-0.05.

Such polysaccharides can be prepared by cationic and aromatic denaturation of polysaccharides in a known manner using one or more reagents containing cationic groups or aromatic groups, for example in the presence of alkaline substances such as alkali or alkaline earth metal hydroxides. The saccharide is reacted with the reagent. Polysaccharides subject to cationic and aromatic modifications are non-ionic, anionic, amphoteric or cationic. Suitable denaturing reagents include aralkyl halides such as benzyl chloride and benzyl bromide; Reaction products of epichlorohydrin with dialkylamines having one or more substituents including aromatic groups as defined above such as 3-dialkylamino-1,2-epoxypropane; Reaction products of epichlorohydrin with tertiary amines including aromatic groups as defined above, such as alkaryldialkylamines such as dimethylbenzylamine, and aromatic groups such as arylamines such as pyridine and quinoline. Suitable cationic reagents are 2,3-epoxypropyl trialkylammonium halides and halohydroxypropyl trialkylammonium halides such as hydrophobic alkyl is octyl, decyl and dodecyl and lower alkyl is methyl or ethyl 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 ; Alkaryl and lower alkyl groups are halo-hydroxypropyl-N, N-dialkylN-alkarylammonium halides and N-glycidyl-N- (alkaryl) -N, N- as defined above. Dialkylammonium chlorides, in particular N- (3-chloro-2-hydroxypropyl) -N-benzyl-N, N-dimethylammonium; N- (3-chloro-2-hydroxypropyl) pyridinium chloride. Generally, when non-ionic aromatic reagents are used, the starch becomes cationic using cationic reagents known in the art before and after hydrophobization. Examples of suitable cationic or aromatic modifiers and starches modified with aromatic groups and methods for their preparation are described in US Pat. Nos. 4,687,519, 5,463,127; WO 94/24169, European Patent Application 189 935; S.P.Patel, R.G.Patel and V.S.Patel, Starch / Starke, 41 (1989), No. 5, pp.192-196.

In one aspect the cationic organic polymer is selected from monomers having aromatic groups, especially homopolymers and copolymers made from ethylenically unsaturated monomers. Cationic polymers are linear or branched.

Aromatic groups of the cationic polymer may be present in the backbone, attached to, or extended to, the backbone, or present in the backbone attached to or extended to the backbone. Suitable aromatics (aryl) include phenyl (secondary substituted), phenylene (secondary substituted), naphthyl (secondary substituted) and the general formulas -C ₆ H _5- , -C ₆ H _4- , -C ₆ H _3- , -C ₆ H _2- , such as phenylene (-C ₆ H _4- ), xylene (-CH ₂ -C ₆ H ₄ -CH _2- ), phenyl (-C ₆ H _5- ), Benzyl (CH ₂ -C ₆ H ₅ ), phenethyl (-CH ₂ CH ₂ -C ₆ H ₅ ), substituted phenyl (-C ₆ H ₄ -Y, -C ₆₄₃ -Y ₂ , -C ₆ Substituent (Y) comprising H ₂ -Y ₃ ) and attached to the phenyl ring is a hydroxy, halide (chloride), nitro and hydrocarbon group having 1-4 carbon atoms.

In particular cationic polymers are vinyl addition polymers. Vinyl addition polymerization polymers are polymers prepared by addition polymerization of one or more vinyl monomers or ethylenically unsaturated monomers including acrylamide and acrylic based monomers. In particular, the cationic polymer is selected from cationic vinyl addition polymerization polymers obtained by polymerizing cationic monomers including cationic monomers of formula (4).

Wherein R ₁ is H or CH ₃ , R ₂ and R ₃ are alkyl groups having 1-3, in particular 1-2 carbon atoms, A ₁ is O or NH, B ₁ is 2-8, in particular 2 -Is an alkylene or hydroxy propylene group having 4 carbon atoms, Q is a phenyl or substituted group which can be attached to nitrogen by means of an aromatic group containing substituent, in particular 1-3, furthermore an alkylene group having 1-2 carbon atoms Phenyl, benzyl group (CH ₂ -C ₆ H ₅ ) is preferred, and X ⁻ is an anionic counter ion, halide, especially chloride. Monomers of formula 4 include dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dimethylaminohydroxypropyl (meth) acrylate and dimethylaminoethyl ( Dialkylaminoalkyl (meth) acrylamides such as meta) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide are treated with benzyl chloride. Quaternary monomers obtained. Preferred cationic monomers of formula 4 are dimethylaminoethyl acrylate benzyl chloride quaternary salt and dimethylaminoethyl methacrylate benzyl chloride quaternary salt.

The cationic vinyl addition polymer may be a copolymer prepared from a monomer mixture comprising a cationic monomer having an aromatic group and at least one copolymerizable monomer or a homopolymer prepared from a cationic monomer having an aromatic group. Suitable copolymerizable non-ionic monomers include monomers of formula (5).

Wherein R ₅ is H or CH ₃ , R ₆ and R ₅ are hydrocarbon groups, especially alkyl groups having 1-6, especially 1-4, even 1-2 carbon atoms, A ₂ is O or NH, B ₂ is an alkylene or hydroxy propylene group having 2-8, in particular 2-4 carbon atoms, or A and B have a single bond between C and N (O = C—NR ₅ R ₆ ). Examples of suitable copolymerizable monomers include (meth) acrylamide; Acrylamide-based monomers such as N-alkyl (meth) acrylamide and N, N-dialkyl (meth) acrylamide, such as Nn-propylacrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) Acrylamide, N-isobutyl (meth) acrylamide and Nt-butyl (meth) acrylamide; Dialkylaminoalkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide; Acrylic base monomers such as dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate and dimethylaminohydroxy Propyl (meth) acrylate; Vinyl amide, row N-vinylformamide, N-vinylacetamide. Preferred monomers include acrylamide and methacrylamide and the main polymer is an acrylamide based polymer.

Suitable copolymerizable non-ionic monomers include monomers of formula (6).

Wherein R ₇ is H or CH ₃ , R ₈ , R ₉ and R ₁₀ are hydrocarbon groups, especially alkyl groups having 1-3 and even 1-2 carbon atoms, A ₃ is O or NH and B ₃ is Alkylene or hydroxy propylene groups having 2-8, in particular 2-4 carbon atoms, X ⁻ is an anionic counterion such as methylsulfate or halide (eg chloride). Examples of suitable copolymerizable cationic monomers include the dialkylaminoalkyl (meth) acrylamides and dialkylaminoalkyls mentioned above prepared using an acid such as HCl or sulfuric acid or a quaternization reagent such as methyl chloride, dimethyl sulfate. Acid addition salts of meta) acrylates are quaternary ammonium salts and dialkyldimethylammonium chlorides. Copolymerizable anionic monomers such as acrylic acid, methacrylic acid, various sulfonated vinyl addition polymerization monomers can be used in small amounts.

Cationic vinyl addition polymers include monomers of formula (4) having 1-99, in particular 2-50, more preferably 5-20 mol% of aromatic groups, and 99-1, especially 98-50, even 95-80 mol% of acrylamide, It is prepared from a monomer mixture comprising copolymerizable monomers including methacrylamide. The monomer mixture comprises 98-50, in particular 95-80 mole% (meth) acrylamide and the sum is 100%.

The cationic polymer may be selected from polymers prepared by condensation reaction of monomers containing aromatic groups. Examples of such monomers include toluene diisocyanate, bisphenol A, phthalic acid, phthalic anhydride, which can be used to prepare cationic polyurethanes or cationic polyamideamines.

Alternatively, the cationic polymer may be a polymer subjected to aromatic modification using a reagent containing an aromatic group. Suitable denaturing agents are benzyl chloride, benzyl bromide, N- (3-chloro-2-hydroxypropyl) -N-benzyl-N, N-dimethylammonium chloride and N (3-chloro-2-hydroxypropyl) pyridinium chloride It includes. Suitable polymers for such aromatic modifications include vinyl addition polymers. The use of such reagents makes the polymer cationic if the polymer contains tertiary nitrogen which may be quaternized by the denaturant. Alternatively, the polymer to be subjected to aromatic modification may be cationic like the cationic vinyl addition polymer.

Usually the charge density of cationic polymers is 0.1-6.0 per gram of dry polymer, in particular 0.2-4.0, even 0.5-3.0 meqv. The weight average molecular weight of the synthetic polymers is at least 500,000, in particular at least 1,000,000, even more than 2,000,000. The upper limit is not critical and is about 50,000,000, in particular 30,000,000, even 25,000,000.

Anionic polymer

Anionic polymers having one or more aromatic groups included in the sizing promoter may also be present in the sizing dispersion and are selected from condensation polymers, polysaccharides and natural aromatic polymers. Condensation polymers are polymers obtained by condensation polymerization. If the anionic polymer is not a melamine sulfonic acid condensation polymer, the anionic polymer has an aromatic group. Anionic polymers are condensation polymers or natural aromatic polymers. The anionic polymers of the present invention may be linear, branched or crosslinked. In particular anionic polymers are water soluble or water dispersible. Organic polymers are preferred.

Preferred anionic aromatic polymers are naphthalene sulfonate condensation polymers, polystyrene sulfonate polymers and modified lignin polymers and more preferred are modified lignin polymers such as lignin sulfonate and naphthalene sulfonate condensation polymers such as condensed naphthalene sulfonate.

The aromatic group of the anionic polymer may be present in the polymer backbone or substituents attached to the backbone. Examples of suitable aromatic groups include aryl, alkaryl and aralkyl groups such as phenyl, phenylene, naphthyl, xylene, benzyl and phenylethyl and derivatives thereof. Anionic groups that may be present in the anionic polymers and monomers used to make them include anionic charges and acid groups that have anionic charges when dissolved or dispersed in water, such as phosphate, phosphonate, sulfate, sulfonic acid, sulfo Nate, carboxylic acid, carboxylate, alkoxide and phenol groups, ie hydroxy substituted phenyl and naphthyl. Groups with negative charge are salts of alkali metals, alkaline earth metals or ammonia.

Suitable anionic condensation products include condensation polymers, for example condensates of aldehydes such as formaldehyde with aromatic compounds having one or more anionic groups and other co-monomers useful for condensation polymerization such as urea, especially condensed naphthalene sulfonate polymers. . Examples of aromatic compounds having anionic groups include phenol and naphthol compounds such as phenol, naphthol, resorcinol and derivatives thereof, aromatic acids and salts such as phenyl, phenol, naphthyl and naphthol acid and salts, such as benzene sulfonic acid and sulfonate, Sulfonic acids and sulfonates such as xylene sulfonic acid and sulfonate, naphthalene sulfonic acid and sulfonate, phenol sulfonic acid and sulfonate.

Further suitable anionic polycondensation products include anionic polyurethanes prepared from polymers obtained by condensation addition polymerization, such as monomer mixtures comprising aromatic isocyanates or aromatic alcohols. Suitable aromatic isocyanates include diisocyanates such as toluene-2,4- and 2,6-diisocyanate and diphenyl-methane-4,4'-diisocyanate. Suitable aromatic alcohols include diols such as bisphenol A, phenyl diethanol amines, glycerol monoterephthalate and trimethylolpropane monoterephthalate. Monovalent aromatic alcohols such as phenol and derivatives thereof can be used. The monomer mixture may also include alcohols or non-aromatic isocyanates such as diisocyanates and diols known in polyurethane production. Suitable monomers containing anionic groups are monoester reaction products of triols such as trimethylolethane, trimethylolpropane and glycerol with dicarboxylic acids and anhydrides such as succinic and anhydrides, terephthalic acid and anhydrides, such as glycerol monosuccinate, glycerol monotere Phthalate, trimethylolpropane monosuccinate, trimethylolpropane monoterephthalate, N, N-bis- (hydroxyethyl) -glycine, di- (hydroxymethyl) propionic acid, N, N-bis- (hydroxyethyl) 2-aminoethanesulfonic acid, which reacts with alkali and alkaline earth metal hydroxides such as sodium hydroxide, amines such as triethylamine, and bases such as ammonia to form alkali and alkaline earth metals or ammonium counterions.

Suitable anionic polycondensation products are usually copolymerized with acrylate- and acrylamide based monomers and anionic vinyl additions obtained from a mixture of vinyl or ethylenically unsaturated monomers comprising at least one monomer having an aromatic group and at least one monomer having an anionic group. Polymerized polymers. Suitable anionic monomers include (meth) acrylic acid and paravinyl phenol (hydroxy styrene).

Suitable anionic polysaccharides are cationic polysaccharides such as starch, guar gum, cellulose, chitin, chitosan, glycan, galactan, glucan, xan gum, pectin, mannan, dextrin, and starch and guar gum Preferred, starch is potato, corn, wheat, tapioca, rice, waxed corn, barley. In polysaccharides anionic groups are either present or introduced by chemical means. Aromatic groups of polysaccharides are introduced by known chemical methods.

Natural aromatic anionic polymers of the present invention include kraft lignin, such as modified lignin polymers copolymerized with formaldehyde and sulfonated lignin, such as tannin extracts such as lignin sulfonates and natural polyphenol compounds present in wood extracts.

The weight average molecular weight of the anionic polymer is at least 500, in particular at least 2000, even more than 5000. The upper limit is not critical and is about 20,000,000, in particular 15,000,000, even 1,000,000.

Anionic polymers can have a wide range of degrees of substitution and anionic degrees of substitution (DS _A ) are 0.01-2.0, in particular 0.02-1.8, even 0.025-1.5. The aromatic substitution degree (DS _H ) is 0.001-1.0, in particular 0.01-0.8, even 0.02-0.7 and when the anionic polymer contains a cationic group, the cationic degree of substitution (DS _C ) is 0-0.2, in particular 0-0.1, Furthermore, it is 0-0.05 and the anionic polymer has a negative total charge. The negative charge density of the anionic polymer is 0.1-6.0 per gram of dry polymer, in particular 0.5-5.0, even more 1.0-4.0 meqv.

The anionic polymer having an aromatic group of the sizing accelerator and the cationic organic polymer having an aromatic group may be added to the aqueous suspension separately from the sizing dispersion in various amounts depending on the type of the stock solution, the salt content, the kind of the salt, the filler content, and the timing of the addition. Generally, polymers are added in an amount that gives a better sizing effect if they are not added and cationic organic polymers are added before anionic polymers. The cationic polymer is added in an amount of at least 0.001%, in particular at least 0.005% by weight, based on the dry stock material, with an upper limit of 3%, in particular 2.0% by weight. The anionic polymer is added in an amount of at least 0.001%, in particular at least 0.005% by weight relative to the dry stock material, with an upper limit of 3%, in particular 1.5% by weight.

Apart from cationic organic polymers and anionic polymers, sizing promoters include anionic microparticles such as silica based particles and smectite clay, low molecular weight cationic organic polymers, alum, aluminate, aluminum chloride, aluminum nitrate and polyaluminum compounds (poly Aluminum compounds such as aluminum chloride, polyaluminum sulfate, polyaluminum compounds containing chlorine and sulfate ions, polyaluminum silicate-sulfate and mixtures thereof), and other compounds that increase the sizing efficiency, such as anionic vinyl addition polymerization polymers.

The process of the present invention is used to make paper from high conductivity stock solutions containing cellulose fibers and fillers. The conductivity of the stock solution is at least 0.20 mS / cm, in particular at least 0.5 mS / cm, even more than 3.5 mS / cm. Very good results are observed at conductivity greater than 5.0 mS / cm and even greater than 7.5 mS / cm. Conductivity can be measured with standard equipment such as the WTW LF 539 instrument supplied by Christiian Berner. The above mentioned values can be determined by measuring the conductivity of the cellulose suspension present or supplied in the head box of the paper machine or by measuring the conductivity of the white water obtained by suspension dehydration. High conductivity refers to a high content of salts (electrolytes) and salts are alkali metals (Na ⁺ , K ⁺ ), alkali metals (Ca ²⁺ , Mg ²⁺ ), aluminum ions (Al ³⁺ , Al (OH) ²⁺ ) and unit price, such as poly aluminum ion, divalent -, and multivalent-cation, a halide (Cl ^_), sulfate _{^{(SO 4 2-, HSO 4 -}} ), carbonate _{^{(CO 3 2-, HCO 3 -}} ), Mono-, di-, and poly-anions such as silicates and lower organic acids. Dispersions are useful for making paper from stocks containing high content, at least 200 ppm, in particular at least 300 ppm, even more than 400 ppm of divalent and polyvalent cation salts. The salts can be derived from the cellulose fibers and fillers used in the stock forming, especially in integrated plants where concentrated aqueous fiber suspensions from pulp mills are mixed with water to form a thin suspension suitable for paper production at paper mills. In addition, salts may be derived or intentionally added from various additives introduced into the stock solution, fresh water supplied to the process. In addition, the salt content is higher in processes where white water is recycled excessively, accumulating more salt in the water circulating in the process.

The present invention is a papermaking machine in which fresh water of 0-30 tons, usually less than 20 tons, in particular less than 15 tons, even less than 10 tons and even less than 5 tons is used per tonne of paper produced, which is excessively recycled to a high degree of closure. It is useful in the process. Recycling the white water obtained in the process includes mixing the white water with the cellulose fibers and the filler to form a suspension to be sized and mixing the white water with the cellulose fibers and the filler before the suspension is introduced into the forming wire for sizing. do.

In papermaking processes such as dry strength enhancers and wet strength enhancers, traditional additional additives may be used in combination with the additives according to the invention. Cellulose suspensions include kaolin, china clay, titanium dioxide, gypsum, talc, natural and synthetic calcium carbonates (eg chalk, marble powder and precipitated calcium carbonate).

The process of the present invention can be used as a sizing agent in all kinds of cell paper processes. Paper includes not only paper but also cellulose based products in the form of sheets and webs such as boards and cardboard. The process can be used to make paper from different types of cellulosic fiber suspensions, the suspension containing at least 25%, in particular at least 50%, by weight of cellulose fibers relative to the dry matter. The suspensions are sulfate, sulfite and organosolve pulp. Chemical pulp, such as chemical pulp, mechanical pulp such as thermomechanical pulp, refined pulp and wood pulp, and may be based on recycled fibers from ink removed pulp. The present invention is useful for making paper from suspensions based on pulp, including de-pulled pulp and recycled fibers, with cellulosic fiber content of up to 100%, in particular 20-100%.

Example 1

The sizing performance of this process is evaluated using the cobb 60 test. Anionic sizing dispersions containing alkyl ketene dimers, condensed naphthalene sulfonates and di (hydrogenated resin) dimethyl ammonium chloride are prepared. The sizing dispersion has an AKD content of 30% and contains 4% di (hydrogenated resin) dimethyl ammonium chloride and 6% condensed naphthalene sulfonate relative to AKD. The sizing dispersion is added in an AKD amount of 5 kg per tonne of dry stock solution.

Condensed naphthalene sulfonates commercially available with Tamol included in cationic starch with 0.065 cationic substitution DS and nitrogen sizing accelerator for nitrogen containing benzyl groups are added. Added to the furnish. In addition, additional components included in the sizing promoter are added to the stock solution shown in Table 1 including the aromatic group non-containing cationic starch having a DS of 0.065 and inorganic silica particles provided as a sol.

The furnish used is based on 80% bleached birch / pine (60/40) sulphate pulp and 20% calcium carbonate, refined to 200 CSF, contains 0.3 g / l stock sodium sulfate, 461 μS / cm conductivity and 8.1 Furnishes with pH are used.

Test number Anionic Sizing Dispersion [kg of sizing agent / toning dry stock solution] Aromatic group-containing cationic starch [kg / tonne dry stock solution] Aromatic group Non-cationic starch [starch kg / tonne dry stock] Test 1 0.5 0 10 Test 2 0.5 10 0 Test 3 0.5 10 0

Test number Condensed naphthalenesulfonate [kg / tonne dry stock] Anionic silica particles [silica kg / ton of dry stock] cobb 60 [g / ㎡] Test 1 0 One 45.2 Test 2 0 One 33.5 Test 3 One 0 29.3

Example 2

The sizing performance of this process was evaluated using the cobb 60 test using the same anionic sizing dispersion, sizing promoter and stock solution as in Example 1 but adding calcium chloride to adjust the conductivity to 5000 μS / cm. The amount of promoter polymer and sizing agent (AKD) is shown in Table 2.

Test number Anionic Sizing Dispersion [kg of sizing agent / toning dry stock solution] Aromatic group-containing cationic starch [kg / tonne dry stock solution] Aromatic group Non-cationic starch [starch kg / tonne dry stock] Test 1 0.5 0 10 Test 2 0.5 12 0 Test 3 0.5 10 0

Test number Condensed naphthalenesulfonate [kg / tonne dry stock] Anionic silica particles [silica kg / ton of dry stock] cobb 60 [g / ㎡] Test 1 0 1.0 75 Test 2 0 1.0 28 Test 3 One 0 27.8

Example 3

An anionic sizing dispersion is prepared containing 8.9 wt% commercial alkyl ketene dimer, aromatic substituted cationic starch containing 0.89 wt% benzyl group (DS: 0.065), and 0.22 wt% condensed naphthalene sulfonate sold as Tamol. . The anionic dispersions contained 0.0115- as shown in Table 1 for ketene dimers in a cellulose suspension (dry base) containing 30% pine, 30% beech, 40% eucalyptus and 15% precipitated calcium carbonate. It is added in an amount of 0.0140% by weight (dry base, Table 3). The conductivity of the suspension is 500 μS / cm. To the suspension is also added a sizing promoter containing benzyl substituted starch having 0.065 DS and a condensed naphthalene sulfonate sold as Tamol. The same anionic dispersion is added to the same cellulose suspension but the sizing promoter added to the suspension contains a non-aromatic polymer. Sizing promoters include anionic inorganic silica particles (test 1), which are provided as cationic starch and sol of aromatic group-free DS0.065. The amount of sizing agent (AKD) of the polymer and the dispersion of the promoter is shown in Table 3.

Test number Anionic Sizing Dispersion [kg of sizing agent / toning dry stock solution] Aromatic group-containing cationic starch [kg / tonne dry stock solution] Aromatic group Non-cationic starch [starch kg / tonne 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 number Condensed naphthalenesulfonate [kg / tonne dry stock] Anionic silica particles [silica kg / ton of dry stock] cobb 60 [g / ㎡] 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

The same dispersions, sizing promoters and suspensions (stock solutions) as in Example 3 were used except that the conductivity of the suspension was 5000 μS / cm. The amount of promoter polymer and sizing agent (AKD) is shown in Table 4.

Test number Anionic Sizing Dispersion [kg of sizing agent / toning dry stock solution] Aromatic group-containing cationic starch [kg / tonne dry stock solution] Aromatic group Non-cationic starch [starch kg / tonne 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 number Condensed naphthalenesulfonate [kg / tonne dry stock] Anionic silica particles [silica kg / ton of dry stock] cobb 60 [g / ㎡] 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

Sizing performance is assessed using a cationic sizing dispersion comprising 15% by weight AKD, 2% cationic starch and 0.6% sodium lignosulfonate for the sizing agent AKD. Cationic sizing dispersion is added to the stock solution in an amount of 0.5 kg sizing agent per tonne of dry stock solution. The polymers included in the sizing promoter (Table 5) contain anionic inorganic silica particles provided as condensed naphthalene sulfonates, cationic starches without aromatic groups (DS 0.065), cationic starches containing aromatic groups (DS 0.065) and sol. Include. The amount of polymer added to the promoter is shown in Table 5. The stock solution used was the same as in Example 2 with the addition of calcium chloride and a pH of 8.1 to adjust the conductivity to 5000 μS / cm.

Test number Anionic Sizing Dispersion [kg of sizing agent / toning dry stock solution] Aromatic group-containing cationic starch [kg / tonne dry stock solution] Aromatic group Non-cationic starch [starch kg / tonne dry stock] Test 1 0.5 0 10 Test 2 0.5 0 10 Test 3 0.5 10 0

Test number Condensed naphthalenesulfonate [kg / tonne dry stock] Anionic silica particles [silica kg / ton of dry stock] cobb 60 [g / ㎡] Test 1 0 One 55 Test 2 One 0 34 Test 3 One 0 27.8

Example 6

The sizing performance of this process is evaluated using the cobb 60 test. Anionic sizing dispersions containing alkyl ketene dimers, condensed naphthalene sulfonates and di (hydrogenated resin) dimethyl ammonium chloride are prepared. The sizing dispersion has an AKD content of 30% and contains 4% di (hydrogenated resin) dimethyl ammonium chloride and 6% condensed naphthalene sulfonate relative to AKD. The sizing dispersion is added in an AKD amount of 0.3 kg per tonne of dry stock.

Sizing promoters include cationic starches with benzyl group containing cation substituted DS of 0.065, non-aromatic starches with cation substituted DS of 0.065, condensed naphthalene sulfonate and melamine sulfonate. The sizing accelerator and the amount of polymer added to the accelerator are shown in Table 6.

The furnish used is based on 80% bleached birch / pine (60/40) sulphate pulp and 20% calcium carbonate, refined to 200CSF, contains 0.3 g / l undiluted sodium sulphate and a conductivity of 555 μS / cm and 8.22. Furnishes with pH are used.

Test number Anionic Sizing Dispersion [kg of sizing agent / toning dry stock solution] Aromatic group-containing cationic starch [kg / tonne dry pulp] Aromatic group Non-cationic starch [starch kg / tonne dry stock] Test 1 0.3 10 Test 2 0.3 10 Test 3 0.3 0 Test 4 0.3 0

Test number Condensed naphthalenesulfonate [kg / tonne dry pulp] Melaninsulfonate [kg / dry pulp tone] cobb 60 [g / ㎡] Test 1 One 33 Test 2 One 52 Test 3 One 35 Test 4 One 68

Claims (100)

In an aqueous suspension containing cellulose fibers and fillers i) an sizing agent, an aqueous sizing dispersion comprising a polymer having at least one aromatic group and ii) adding a sizing accelerator comprising a polymer having at least one aromatic group, A paper sizing method comprising the steps of forming and dehydrating the obtained suspension, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. The paper sizing method of claim 1, wherein the sizing dispersion is anionic or cationic. The method of claim 1 wherein the sizing agent is a cellulose reactive sizing agent. The paper sizing method according to claim 3, wherein the sizing agent is a ketene dimer or anhydrous acid. The paper sizing method according to claim 3, wherein the sizing agent is a ketene dimer. The method of claim 1 wherein the polymer having at least one aromatic group included in the sizing dispersion is charged. The method of claim 1 wherein the polymer having at least one aromatic group included in the sizing dispersion is anionic or cationic. In an aqueous suspension containing cellulose fibers and fillers i) an sizing agent, an aqueous sizing dispersion comprising a polymer having at least one aromatic group and ii) adding a sizing promoter comprising a first polymer having at least one aromatic group and a second polymer having at least one aromatic group, A paper sizing method comprising the steps of forming and dehydrating the obtained suspension, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. 9. The paper sizing method of claim 8, wherein the first and second polymers of sizing promoter are added separately. 9. The paper sizing method of claim 8, wherein the sizing dispersion is anionic or cationic. 9. The paper sizing method of claim 8 wherein the sizing agent is a cellulose reactive sizing agent. 12. The paper sizing method according to claim 11, wherein the sizing agent is a ketene dimer or anhydrous acid. 12. The paper sizing method of claim 11 wherein the sizing agent is a ketene dimer. 9. The paper sizing method of claim 8, wherein the first and second polymers included in the sizing promoter are charged. 9. The paper sizing method of claim 8, wherein the total charge of the first and second polymers included in the sizing promoter is opposite. In an aqueous suspension containing cellulose fibers and fillers i) an sizing agent, an aqueous sizing dispersion comprising a polymer having at least one aromatic group and ii) adding a sizing promoter comprising a cationic organic polymer having at least one aromatic group and an anionic polymer having at least one aromatic group selected from condensation polymers, polysaccharides or natural aromatic polymers, A paper sizing method comprising the steps of forming and dehydrating the obtained suspension, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. 17. The paper sizing method of claim 16, wherein the sizing dispersion is anionic or cationic. 17. The paper sizing method of claim 16 wherein the sizing agent is a cellulose reactive sizing agent. 19. The paper sizing method according to claim 18, wherein the sizing agent is a ketene dimer or anhydrous acid. 19. The paper sizing method of claim 18, wherein the sizing agent is a ketene dimer. 17. The paper sizing method of claim 16 wherein the cationic organic polymer of the sizing promoter is a cationic polysaccharide or a cationic vinyl addition polymer. The method of claim 16 wherein the cationic organic polymer of the sizing accelerator is a cationic polysaccharide. 17. The method of claim 16 wherein the anionic polymer of the sizing promoter is a condensation polymer or a naturally aromatic polymer. The method of claim 16 wherein the anionic polymer of the sizing promoter is a naphthalene sulfonate condensation polymer or a modified lignin polymer. The paper sizing method of claim 24 wherein the anionic polymer of the sizing promoter is a condensed naphthalene sulfonate or lignin sulfonate. 22. The paper sizing method according to claim 21, wherein the cationic organic polymer is a cationic polysaccharide of formula (3) or a vinyl addition polymer obtained by polymerizing a cationic monomer of formula (4). Wherein P is a residue of the polysaccharide, A is an atom chain containing C and H atoms as a group to attach N to the polysaccharide residue, R ₁ and R ₂ are H or a hydrocarbon group, and R ₃ is an aromatic hydrocarbon Group, n is 2-300,000, X ⁻ is an anionic counter ion, Wherein R ₁ is H or CH ₃ , R ₂ and R ₃ are alkyl groups having 1-3 carbon atoms, A ₁ is O or NH, B ₁ is alkylene or hydroxy propylene having 2-8 carbon atoms Group, Q is an aromatic group containing substituent, and X ⁻ is an anionic counter ion. 23. The method of claim 22, wherein the cationic organic polymer is a cationic polysaccharide of formula Wherein P is a residue of the polysaccharide, A is an atom chain containing C and H atoms as a group to attach N to the polysaccharide residue, R ₁ and R ₂ are H or a hydrocarbon group, and R ₃ is an aromatic hydrocarbon Group, n is 2-300,000 and X ⁻ is an anionic counter ion. 28. The compound of claim 27, wherein A is an alkylene group which may be substituted with one or more heteroatoms and contains 2-18 carbon atoms, R ₁ and R ₂ are H or an alkyl group containing 1-3 carbons, and R ₃ is benzyl Or phenylethyl paper sizing method 17. The paper sizing method of claim 16, wherein the cationic organic polymer and the anionic polymer included in the sizing promoter are added separately to the aqueous suspension. 17. The paper sizing method of claim 16, wherein the anionic polymer included in the sizing promoter is added to the aqueous suspension after the cationic organic polymer included in the sizing dispersion and the sizing promoter. 17. The paper sizing method of claim 16 wherein the conductivity of the suspension is at least 3.5 mS / cm. 17. The paper sizing method of claim 16, wherein the conductivity of the suspension is at least 4.5 mS / cm. In an aqueous suspension containing cellulose fibers and fillers i) 0.01-5.0% by weight of an aqueous sizing dispersion comprising an anionic polymer having at least one aromatic group selected from sizing agents, condensation polymers, polysaccharides or natural aromatic polymers (calculated as sizing agent for dry fibers) and ii) 0.001-3% by weight of cationic organic polymer having at least one aromatic group (relative to dry fibers) and 0.001-3% by weight of anionic polymer having at least one aromatic group selected from condensation polymers, polysaccharides or natural aromatic polymers (dry) Add sizing accelerator (including to the fiber), A paper sizing method comprising the steps of forming and dehydrating the obtained suspension, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. 34. The method of claim 33, wherein the cationic organic polymer is a cationic polysaccharide or cationic vinyl addition polymer. 34. The paper sizing method of claim 33, wherein the cationic organic polymer is a cationic polysaccharide. 35. The paper sizing method of claim 34, wherein the cationic organic polymer is a cationic polysaccharide of formula (3) or a vinyl addition polymerization polymer obtained by polymerizing a cationic monomer of formula (4). Wherein P is a residue of the polysaccharide, A is an atom chain containing C and H atoms as a group to attach N to the polysaccharide residue, R ₁ and R ₂ are H or a hydrocarbon group, and R ₃ is an aromatic hydrocarbon Group, n is 2-300,000, X ⁻ is an anionic counter ion, Wherein R ₁ is H or CH ₃ , R ₂ and R ₃ are alkyl groups having 1-3 carbon atoms, A ₁ is O or NH, B ₁ is alkylene or hydroxy propylene having 2-8 carbon atoms Group, Q is an aromatic group containing substituent, and X ⁻ is an anionic counter ion. 36. The method of claim 35, wherein the cationic organic polymer is a cationic polysaccharide of formula Wherein P is a residue of the polysaccharide, A is an atom chain containing C and H atoms as a group to attach N to the polysaccharide residue, R ₁ and R ₂ are H or a hydrocarbon group, and R ₃ is an aromatic hydrocarbon Group, n is 2-300,000 and X ⁻ is an anionic counter ion. 38. The compound of claim 37, wherein A is an alkylene group which may be substituted with one or more heteroatoms and contains 2-18 carbon atoms, R ₁ and R ₂ are H or an alkyl group containing 1-3 carbons, and R ₃ is benzyl Or phenylethyl paper sizing method 34. The paper sizing method of claim 33, wherein the anionic polymer of the sizing promoter and the dispersion is a condensation polymer or a naturally aromatic polymer. 40. The paper sizing method of claim 39, wherein the anionic polymer is a naphthalene sulfonate condensation polymer, a polystyrene sulfonate polymer or a modified lignin polymer. 40. The method of claim 39 wherein the anionic polymer is a naphthalene sulfonate condensation polymer or a modified lignin polymer. 40. The method of claim 39 wherein the anionic polymer is a condensed naphthalene sulfonate or lignin sulfonate. 34. The paper sizing method of claim 33, wherein the cationic organic polymer and the anionic polymer included in the sizing promoter and the dispersion are added separately to the aqueous suspension. 34. The paper sizing method of claim 33, wherein the anionic polymer included in the sizing promoter is added to the aqueous suspension after the cationic organic polymer included in the sizing dispersion and the sizing promoter. 34. The paper sizing method of claim 33, wherein the conductivity of the suspension is at least 3.5 mS / cm. 46. The paper sizing method of claim 45, wherein the conductivity of the suspension is at least 4.5 mS / cm. 34. The paper sizing method of claim 33, wherein the sizing agent is a cellulose reactive sizing agent. In an aqueous suspension containing cellulose fibers and fillers i) 0.01-5.0% by weight of an aqueous sizing dispersion comprising a sizing agent, a cationic organic polymer having at least one aromatic group and an anionic polymer having at least one aromatic group selected from condensation polymers, polysaccharides or natural aromatic polymers (in dry fibers Calculated as a sizing agent) ii) 0.001-3% by weight of cationic organic polymer having at least one aromatic group (relative to dry fibers) and 0.001-3% by weight of anionic polymer having at least one aromatic group selected from condensation polymers, polysaccharides or natural aromatic polymers (dry) Add sizing accelerator (including to the fiber), A paper sizing method comprising the steps of forming and dehydrating the obtained suspension, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. 49. The paper sizing method of claim 48, wherein the cationic organic polymer of the sizing promoter and dispersion is a cationic polysaccharide or a cationic vinyl addition polymer. 49. The paper sizing method of claim 48, wherein the cationic organic polymer of the sizing promoter and dispersion is a cationic polysaccharide. 50. The method of claim 49, wherein the cationic organic polymer is a cationic polysaccharide of formula (3) or a vinyl addition polymerization polymer obtained by polymerizing a cationic monomer of formula (4). Wherein P is a residue of the polysaccharide, A is an atom chain containing C and H atoms as a group to attach N to the polysaccharide residue, R ₁ and R ₂ are H or a hydrocarbon group, and R ₃ is an aromatic hydrocarbon Group, n is 2-300,000, X ⁻ is an anionic counter ion, Wherein R ₁ is H or CH ₃ , R ₂ and R ₃ are alkyl groups having 1-3 carbon atoms, A ₁ is O or NH, B ₁ is alkylene or hydroxy propylene having 2-8 carbon atoms Group, Q is an aromatic group containing substituent, and X ⁻ is an anionic counter ion. 51. The paper sizing method of claim 50, wherein the cationic organic polymer is a cationic polysaccharide of formula Wherein P is a residue of the polysaccharide, A is an atom chain containing C and H atoms as a group to attach N to the polysaccharide residue, R ₁ and R ₂ are H or a hydrocarbon group, and R ₃ is an aromatic hydrocarbon Group, n is 2-300,000 and X ⁻ is an anionic counter ion. The compound of claim 52, wherein A is an alkylene group which may be substituted with one or more heteroatoms and contains 2-18 carbon atoms, R ₁ and R ₂ are H or an alkyl group containing 1-3 carbons, and R ₃ is benzyl Or phenylethyl paper sizing method 49. The paper sizing method of claim 48, wherein the anionic polymer of the sizing promoter and the dispersion is a condensation polymer or a naturally 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. 55. The paper sizing method of claim 54, wherein the anionic polymer is a naphthalene sulfonate condensation polymer or a modified lignin polymer. 55. The paper sizing method of claim 54, wherein the anionic polymer is a condensed naphthalene sulfonate or lignin sulfonate. 49. The paper sizing method of Claim 48, wherein the cationic organic polymer and the anionic polymer included in the sizing promoter and the dispersion are added separately to the aqueous suspension. 34. The paper sizing method of claim 33, wherein the anionic polymer included in the sizing promoter is added to the aqueous suspension after the cationic organic polymer included in the sizing dispersion and the sizing promoter. 49. The paper sizing method of claim 48, wherein the conductivity of the suspension is at least 3.5 mS / cm. 61. The paper sizing method of claim 60, wherein the conductivity of the suspension is at least 4.5 mS / cm. 49. The paper sizing method of Claim 48, wherein the sizing agent is a cellulose reactive sizing agent. In an aqueous suspension containing cellulose fibers and fillers i) 0.01-5.0% by weight of an aqueous sizing dispersion comprising a sizing agent and an anionic polymer having at least one aromatic group selected from naphthalene sulfonate condensation polymer, polystyrene sulfonate polymer or modified lignin polymer (calculated as sizing agent for dry fibers) )and ii) 0.001-3% by weight of cationic organic polymer having at least one aromatic group (relative to dry fibers) and anionic polymer having at least one aromatic group selected from naphthalene sulfonate condensation polymer, polystyrene sulfonate polymer or modified lignin polymer Add a sizing accelerator containing 3% by weight (relative to dry fibers), A paper sizing method comprising the steps of forming and dehydrating the obtained suspension, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. 64. The method of claim 63, wherein the cationic organic polymer is a cationic polysaccharide of Formula 3 Wherein P is a residue of the polysaccharide, A is an atom chain containing C and H atoms as a group to attach N to the polysaccharide residue, R ₁ and R ₂ are H or a hydrocarbon group, and R ₃ is an aromatic hydrocarbon Group, n is 2-300,000 and X ⁻ is an anionic counter ion. 65. The compound of claim 64, wherein A is an alkylene group which may be substituted with one or more heteroatoms and contains 2-18 carbon atoms, R ₁ and R ₂ are H or an alkyl group containing 1-3 carbons, and R ₃ is benzyl Or phenylethyl paper sizing method 64. The paper sizing method of claim 63, wherein the anionic polymer of the sizing dispersion and promoter is a naphthalene sulfonate condensation polymer or a modified lignin polymer. 67. The paper sizing method of Claim 66, wherein the anionic polymer is a condensed naphthalene sulfonate or lignin sulfonate. 64. The paper sizing method of claim 63, wherein the cationic organic polymer and the anionic polymer included in the sizing promoter are added separately to the aqueous suspension. 64. The paper sizing method of Claim 63, wherein the anionic polymer included in the sizing promoter is added to the aqueous suspension after the cationic organic polymer included in the sizing dispersion and the sizing promoter. 64. The paper sizing method of claim 63, wherein the conductivity of the suspension is at least 3.5 mS / cm. 64. The paper sizing method of claim 63, wherein the conductivity of the suspension is at least 4.5 mS / cm. 64. The paper sizing method of Claim 63, wherein the sizing agent is a cellulose reactive sizing agent. In an aqueous suspension containing cellulose fibers and fillers i) an aqueous sizing dispersion comprising a sizing agent, a cationic organic polymer having at least one aromatic group, and an anionic polymer having at least one aromatic group selected from naphthalene sulfonate condensation polymer, polystyrene sulfonate polymer or modified lignin polymer. Weight percent (calculated as sizing agent for dry fibers) and ii) 0.001-3% by weight of cationic organic polymer having at least one aromatic group (relative to dry fibers) and anionic polymer having at least one aromatic group selected from naphthalene sulfonate condensation polymer, polystyrene sulfonate polymer or modified lignin polymer. Add a sizing accelerator containing 3% by weight (relative to dry fibers), A paper sizing method comprising the steps of forming and dehydrating the obtained suspension, 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 of Formula 3 Wherein P is a residue of the polysaccharide, A is an atom chain containing C and H atoms as a group to attach N to the polysaccharide residue, R ₁ and R ₂ are H or a hydrocarbon group, and R ₃ is an aromatic hydrocarbon Group, n is 2-300,000 and X ⁻ is an anionic counter ion. 75. The compound of claim 74, wherein A is an alkylene group which may be substituted with one or more heteroatoms and contains 2-18 carbon atoms, R ₁ and R ₂ are H or an alkyl group containing 1-3 carbons, and R ₃ is benzyl Or phenylethyl paper sizing method 74. The paper sizing method of Claim 73 wherein the anionic polymer of the sizing dispersion and promoter is a naphthalene sulfonate condensation polymer or a modified lignin polymer. 77. The method of claim 76, wherein the anionic polymer is a condensed naphthalene sulfonate or lignin sulfonate. 74. The paper sizing method of Claim 73, wherein the cationic organic polymer and the anionic polymer included in the sizing promoter are added separately to the aqueous suspension. 74. The paper sizing method of Claim 73, wherein the anionic polymer included in the sizing promoter is added to the aqueous suspension after the cationic organic polymer included in the sizing dispersion and the sizing promoter. 74. The paper sizing method of claim 73, wherein the conductivity of the suspension is at least 4.5 mS / cm. 74. The paper sizing method of Claim 73, wherein the sizing agent is a cellulose reactive sizing agent. In an aqueous suspension containing cellulose fibers and fillers i) 0.01-5.0% by weight of an aqueous sizing dispersion comprising a sizing agent and an anionic polymer having at least one aromatic group selected from naphthalene sulfonate condensation polymer, polystyrene sulfonate polymer or modified lignin polymer (calculated as sizing agent for dry fibers) )and ii) anionic having 0.001-3% by weight of cationic organic polymer of formula (3) (with respect to dry fibers) having at least one aromatic group and at least one aromatic group selected from naphthalene sulfonate condensation polymer, polystyrene sulfonate polymer or modified lignin polymer Add a sizing accelerator comprising 0.001-3% by weight of polymer (relative to dry fibers), A paper sizing method comprising the steps of forming and dehydrating the obtained suspension, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. Wherein P is a residue of the polysaccharide, A is an atom chain containing C and H atoms as a group to attach N to the polysaccharide residue, R ₁ and R ₂ are H or a hydrocarbon group, and R ₃ is an aromatic hydrocarbon Group, n is 2-300,000 and X ⁻ is an anionic counter ion. 83. The paper sizing method of claim 82, wherein the anionic polymer of the sizing dispersion and promoter is a naphthalene sulfonate condensation polymer or a modified lignin polymer. 84. The method of claim 83, wherein the anionic polymer is a condensed naphthalene sulfonate or lignin sulfonate. 83. The paper sizing method of Claim 82, wherein the cationic organic polymer and the anionic polymer included in the sizing promoter are added separately to the aqueous suspension. 83. The paper sizing method of Claim 82, wherein the anionic polymer included in the sizing promoter is added to the aqueous suspension after the cationic organic polymer included in the sizing dispersion and the sizing promoter. 83. The paper sizing method of claim 82, wherein the conductivity of the suspension is at least 3.5 mS / cm. 83. The paper sizing method of Claim 82, wherein the sizing agent is a cellulose reactive sizing agent. 83. The paper sizing method of claim 82, wherein the sizing agent is present in the dispersion in an amount of 0.1-50% by weight of the total emulsion weight. 83. The paper sizing method of claim 82, wherein the anionic polymer of the sizing dispersion is present in the dispersion in an amount of 0.1-15% by weight relative to the sizing agent. In an aqueous suspension containing cellulose fibers and fillers i) an aqueous sizing dispersion comprising a sizing agent, a cationic organic polymer of formula 3 having at least one aromatic group, and an anionic polymer having at least one aromatic group selected from naphthalene sulfonate condensation polymer, polystyrene sulfonate polymer or modified lignin polymer 0.01-5.0% by weight (calculated as sizing agent for dry fibers) and ii) anionic having 0.001-3% by weight of cationic organic polymer of formula (3) (with respect to dry fibers) having at least one aromatic group and at least one aromatic group selected from naphthalene sulfonate condensation polymer, polystyrene sulfonate polymer or modified lignin polymer Add a sizing accelerator comprising 0.001-3% by weight of polymer (relative to dry fibers), A paper sizing method comprising the steps of forming and dehydrating the obtained suspension, wherein the sizing dispersion and the sizing promoter are added separately to the aqueous suspension. Wherein P is a residue of the polysaccharide, A is an atom chain containing C and H atoms as a group to attach N to the polysaccharide residue, R ₁ and R ₂ are H or a hydrocarbon group, and R ₃ is an aromatic hydrocarbon Group, n is 2-300,000 and X ⁻ is an anionic counter ion. 92. The paper sizing method of claim 91, wherein the anionic polymer of the sizing dispersion and accelerator is a naphthalene sulfonate condensation polymer or a modified lignin polymer. 92. The method of claim 91, wherein the anionic polymer is a condensed naphthalene sulfonate or lignin sulfonate. 92. The paper sizing method of claim 91, wherein the cationic organic polymer and the anionic polymer included in the sizing promoter are added separately to the aqueous suspension. 92. The paper sizing method of claim 91, wherein the anionic polymer included in the sizing promoter is added to the aqueous suspension after the cationic organic polymer included in the sizing dispersion and the sizing promoter. 92. The paper sizing method of claim 91, wherein the conductivity of the suspension is at least 3.5 mS / cm. 92. The paper sizing method of claim 91, wherein the sizing agent is a cellulose reactive sizing agent. 92. The paper sizing method of claim 91, wherein the sizing agent is present in the dispersion in an amount of 0.1-50% by weight of the total emulsion weight. 92. The paper sizing method of claim 91, wherein the anionic polymer of the sizing dispersion is present in the dispersion in an amount of 0.1-15% by weight relative to the sizing agent. 92. The paper sizing method of claim 91, wherein the cationic polymer of the sizing dispersion is present in the dispersion in an amount of 0.1-15% by weight relative to the sizing agent.