CN1237228C - Sizing dispersion - 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

Sizing dispersion

field of invention

The present invention relates to aqueous dispersions of sizing agents comprising starches bearing aromatic groups and condensed sulfonates containing less than 95% by weight of amylopectin. The invention also includes a process for producing the aqueous dispersion and the use of the aqueous dispersion as paper stock or surface size.

Background technique

Aqueous dispersions or emulsions of sizing agents are used in papermaking in order to obtain paper and board with improved resistance to wetting and penetration by various liquids.

A dispersion of sizing agent generally contains an aqueous phase and fine particles or droplets of sizing agent dispersed therein. Dispersions are usually prepared by homogenizing a sizing agent, a water-insoluble material, in an aqueous phase in the presence of a dispersant using high shear forces and relatively high temperatures. Commonly used dispersants include anionic, amphoteric and cationic high molecular weight polymers such as sulfonated oils, starches, polyamines, polyamidoamines and vinyl addition polymers. These polymers can be used alone, together or in combination with other compounds to form dispersant systems. Depending on the total charge of the components of the dispersant system, the sizing dispersion will be either anionic or cationic in nature. The sizing dispersion is usually added to an aqueous suspension containing cellulosic fibers, optional fillers and various additives.

Cellulosic suspensions contain a certain amount of non-fibrous materials such as fillers, colloidal substances, charged polymers and various charged contaminants, i.e. anionic waste, electrolytes, charged polymers, etc. Charged contaminants have an impact on sizing efficiency and generally impair sizing performance. Large amounts of charged contaminants in the suspension, such as high levels of salt, make the suspension increasingly difficult to size, ie to obtain paper with satisfactory sizing properties. Other compounds contained in the unfavorable sizing suspension are various lipophilic wood extracts, which can be derived from recycled fibers and mechanical pulp. Adding bulk sizing often improves sizing, however, resulting in higher costs and increased accumulation of sizing in white water. The buildup of non-fibrous material and any other components present in the suspension is even more pronounced in mills where white water is largely recirculated, while only small amounts of fresh water are introduced into the papermaking process. It is therefore the object of the present invention to further improve sizing. Another object of the present invention is to improve sizing when sizing cellulosic suspensions with high electrical conductivity. A further object of the invention is to improve the stability of the dispersion. Other objects of the present invention will appear hereinafter.

Contents of the invention

Specifically, the present invention discloses the following:

1. Aqueous sizing dispersion comprising sizing agent, starch with aromatic groups and condensed sulfonate, wherein condensed sulfonate is selected from naphthalene, reaction product of naphthalene and cresol, diphenyl ether, toluene The condensation products of aromatic sulfonic acids and aldehydes derived from aromatic compounds in cumene, cresol and phenol, and the starch contains less than 95 wt% amylopectin.

2. The aqueous sizing dispersion according to paragraph 1, wherein the starch has the general formula:

wherein P is a residue of starch; A is an atomic chain including C and H atoms linking N to a polysaccharide residue, _R1 and _R2 are each H or a hydrocarbon group, _R3 is an aromatic hydrocarbon group, and n is 2 to 300,000 is an integer, and X ^- is an anionic counterion.

3. The aqueous sizing dispersion according to item 1 or 2 above, wherein the starch contains 90% by weight or less of amylopectin.

4. The aqueous sizing dispersion according to item 1 or 2 above, wherein the condensed sulfonate is a condensation product of an aromatic sulfonic acid and formaldehyde.

5. The aqueous sizing dispersion according to item 1 or 2 above, wherein the condensed sulfonate is a condensation product of naphthalenesulfonic acid and formaldehyde.

6. The aqueous sizing dispersion according to item 1 or 2 above, wherein the sizing agent is a cellulose-reactive sizing agent.

7. A method for sizing paper, comprising adding a sizing aqueous dispersion containing sizing agent, starch with aromatic groups containing 95% by weight or less amylopectin and condensed sulfonate to the aqueous suspension containing cellulose fibers In a liquid, a suspension formed and dewatered on a papermaking wire, wherein the suspension has a conductivity of at least 0.5 mS/cm, said condensed sulfonate is formed from a reaction product selected from naphthalene, naphthalene and cresol, diphenyl ether, Condensation products of aromatic sulfonic acids and aldehydes derived from aromatic compounds in toluene, cumene, cresol and phenol.

8. A method for sizing paper according to paragraph 7, wherein the starch has the following general formula (I):

wherein P is a residue of starch; A is an atomic chain including C and H atoms linking N to a polysaccharide residue, _R1 and _R2 are each H or a hydrocarbon group, _R3 is an aromatic hydrocarbon group, and n is 2 to 300,000 is an integer, and X ^- is an anionic counterion, the starch contains less than 95% by weight amylopectin.

9. The method of sizing paper according to item 7 or 8 above, wherein the suspension has a conductivity of at least 3.5 mS/cm.

10. The method for sizing paper according to item 7 or 8 above, wherein the starch contains 90% by weight or less of amylopectin.

11. The method for sizing paper according to item 7 or 8 above, wherein the condensed sulfonate is a condensation product of naphthalenesulfonic acid and formaldehyde.

12. The method for sizing paper according to item 7 or 8 above, wherein the sizing agent is a cellulose-reactive sizing agent.

Detailed description of the invention

According to the invention, it was surprisingly found that improved sizing can be obtained with the aqueous dispersions according to the claims. More specifically, the present invention includes aqueous dispersions of starches having aromatic groups and sizing agents of condensation products of aromatic sulfonic acids and aldehydes containing less than 95% by weight of amylopectin. The invention also furthermore includes a process for the preparation of the aqueous dispersion and the use of the dispersion as a paper stock size and surface size.

The sizing agent for the dispersion according to the invention is suitably any known sizing agent, such as a non-cellulose reactive agent, including rosins, such as disproportionated rosins, hydrogenated rosins, polymerized rosins, formaldehyde-treated rosins, esterified rosins, Fortified rosins and mixtures of these treatments and rosins so treated, fatty acids and their derivatives, for example fatty acid esters and amides such as bis-stearamide, resins and their derivatives, for example hydrocarbon resins, resin acids, resin esters and amides, waxes, such as crude and refined paraffin waxes, synthetic waxes, naturally occurring waxes, etc., and/or cellulose reactive agents. Preferably, the size is a cellulose reactive size. The cellulose reactive sizing agent included in the sizing dispersion can be selected from any cellulose reactive agent known in the art. Suitably, the sizing agent is selected from hydrophobic ketene dimers, ketene polymers, anhydrides, organic isocyanates, carbamoyl chlorides and mixtures thereof, preferably ketene dimers, most preferably ketene dimers . Suitable ketene dimers have the following general formula (I), wherein R and ^R represent saturated or unsaturated hydrocarbon groups, usually saturated hydrocarbons, the hydrocarbon groups suitably having 8-36 carbon atoms ^, usually 12-20 carbon atoms Straight-chain or branched-chain alkyl groups of atoms, such as hexadecyl and octadecyl. The ketene dimer may be liquid at ambient temperature, ie at 25°C, conveniently at 20°C. Suitable acid anhydrides can be characterized by the following general formula (II), wherein ^R3 and ^R4 can be the same or different, representing a saturated or unsaturated hydrocarbon group suitably containing 8-30 carbon atoms, or ^R3 and ^R4 and -COC - the moieties are together capable of forming a 5-6 membered ring, optionally further substituted with a hydrocarbyl group containing up to 30 carbon atoms. Examples of industrially used anhydrides include alkyl and alkenyl succinic anhydrides and especially isocadecenyl succinic anhydrides.

Suitable ketene dimers, anhydrides and organic isocyanates include those disclosed in U.S. Patent No. 4,522,686, incorporated herein by reference. Examples of suitable carbamoyl chlorides include those disclosed in U.S. Patent No. 3,887,427, which is also incorporated herein by reference.

The starches contained in the dispersions according to the invention have aromatic groups and contain less than 95% by weight of amylopectin. Starch mainly contains two components, namely amylose and amylopectin. Amylose is a linear polymer, whereas amylopectin is a branched polymer with a molecular weight significantly higher than that of amylose. Preferably, the aromatic starch has an amylopectin content of 92 wt% or less, more preferably 90 wt% or less and still more preferably 85 wt% or less. The starch comprised in the dispersion according to the invention is suitably a cationic starch having aromatic groups, i.e. the cationic starch has at least one aromatic group and at least one cationic group, the cationic group being suitably a tertiary amino group, or Quaternary ammonium groups are preferred. The starch may also contain one or more anionic groups, for example phosphate, phosphonate, sulfate, sulfonate or carboxylic acid groups, which are preferably phosphate groups. Anionic groups, if present, may be present or introduced by chemical treatment in the usual manner. Native potato starch contains a large number of covalently bonded phosphate monoester groups. In amphoteric starches, cationic groups are preferably present in major amounts.

Aromatic groups of starch can be attached to heteroatoms, such as nitrogen or oxygen, which optionally can be charged, for example when it is nitrogen. Aromatic groups can also be attached to groups comprising heteroatoms, such as amides, esters or ethers, which groups can be attached to the polysaccharide backbone (backbone) of starch, eg via a chain of atoms. Examples of suitable aromatic groups and groups including aromatic groups include aryl and aralkyl groups such as phenyl, phenylene, naphthyl, phenylene, xylylenedimethyl, benzyl and phenylene Ethyl; nitrogen-containing aromatic groups (aryls), such as pyridinium and quinolinium, and derivatives of these groups, wherein one or more substituents attached to the aromatic group can be selected from hydroxyl , halogen, such as chloride, nitro, and hydrocarbon groups having 1-4 carbon atoms.

Particularly suitable starches for inclusion in the sizing dispersion include those having the general formula (I):

Wherein P is the residue of starch polysaccharide; A is the group that N is connected to polysaccharide residue, suitably is the atom chain that comprises C and H atom, and optional O and/N atom, usually has 2-18 and suitably An alkylene group of 2-8 carbon atoms, optionally inserted or substituted by one or more heteroatoms (such as O or N), such as alkyleneoxy or hydroxypropylene (- CH ₂ -CH(OH)-CH ₂ -); R ₁ and R ₂ are each H, or preferably a hydrocarbon group, suitably an alkyl group having 1 to 3 carbon atoms, suitably 1 or 2 carbon atoms; R ₃ is Aromatic hydrocarbon groups including aralkyl groups, such as benzyl and phenethyl; n is an integer from about 2 to about 300,000, suitably 5-200,000 and preferably 6-125,000, or additionally R ₁ , R ₂ and R ₃ together with N form an aromatic group containing 5-12 carbon atoms; and X ^- is an anionic counterion, usually a halide such as chloride.

Aromatic group modified cationic or amphoteric starch can have a degree of substitution varying within a wide range; cationic degree of substitution ( _DSc ) can be 0.01-0.5, suitable 0.02-0.3, preferably 0.025-0.2, aromatic degree of substitution (DS _H ) may be 0.01-0.5, suitably 0.02-0.3, preferably 0.025-0.2, and the degree of anionic substitution (DS _A ) may be 0-0.2, suitably 0-0.1, preferably 0-0.05.

These starches can be cationically and aromatically modified in a known manner by means of one or more agents containing cationic and/or aromatic groups, for example by reacting the agent with the starch in an alkaline substance such as a base Prepared by reacting in the presence of metal or alkaline earth metal hydroxides. The starches to be cationically and aromatically modified can be nonionic, anionic, amphoteric or cationic. Suitable modifiers include nonionic agents such as aromatic substituted succinic anhydrides; aralkyl halides such as benzyl chloride and benzyl bromide; epichlorohydrin and compounds having at least one aromatic group comprising as defined above. Reaction products of dialkylamines of substituents, including 3-dialkylamino-1,2-propylene oxide; and cationic agents, such as epichlorohydrin and having at least one substituent comprising an aromatic group as defined above The reaction products of tertiary amines, including trialkylamines, alkaryldialkylamines, such as 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 chlorides and N-glycidyl-N-(hydrophobic alkyl)-N,N-di(lower alkyl)ammonium chlorides, where aromatic The groups are as defined above, especially octyl, decyl and dodecyl, and lower alkyl is methyl or ethyl; and halohydroxypropyl-N,N-dialkyl-N-alkaryl Ammonium halides and N-glycidyl-N-(alkaryl)-N,N-dialkylammonium chlorides such as N-(3-chloro-2-hydroxypropyl)-N-(alkaryl) -N,N-di(lower alkyl)ammonium chloride, wherein alkaryl and lower alkyl are as defined above, especially N-(3-chloro-2-hydroxypropyl)-N-benzyl-N, N-Dimethylammonium chloride; and N-(3-chloro-2-hydroxypropyl)pyridinium chloride. In general, when nonionic aromatic agents are used, the starch is suitably made cationic by using any cationic agent known in the art, either before or after hydrophobic modification. Examples of suitable cationic and/or aromatic modifiers, aromatic group modified starches and methods for their preparation are included in U.S. Patent Nos. 4,687,519 and 5,463,127; International Patent Application WO 94/24169, European Patent Application No. 189 935; and those described in S.P. Patel, R.G. Patel and V.S. Patel, Starch/Störke, 41 (1989), No. 5, pp. 192-196, the teachings of which are incorporated herein by reference.

The starch, suitably cationic or amphoteric, can be present in the dispersion in an amount varying within wide limits, the amount depending inter alia on the molecular weight of the compound, the degree of ionic substitution of the compound, i.e. the charge density, the desired total charge of the dispersion and the hydrophobic material used. Starch can be present in an amount of up to 100 wt%, suitably 0.1-35 wt% and preferably 1-30 wt%, based on the hydrophobic material.

The dispersions according to the invention also comprise condensation sulfonates such as condensation products of aromatic sulfonic acids and aldehydes. The so-called condensed sulfonate refers to a sulfonate obtained through a condensation reaction, and is suitably a polymerized sulfonate. Suitably, the dispersion comprises the condensation product of an aromatic sulfonic acid and formaldehyde. The condensation products are generally polyelectrolytes and are readily soluble in water. A wide variety of aromatic sulfonic acids can be used, such as aromatic sulfonic acids containing one aromatic ring (usually having 6 carbon atoms), and aromatic sulfonic acids containing two or more aromatic rings having 6 carbon atoms acids and fused aromatic sulfonic acids. The aromatic compound is suitably selected from naphthalene, naphthalene reacted with cresol, diphenyl ether, toluene, cumene, cresol, phenol. Typically, the condensation product is formed by reacting the aromatic compound with sulfuric acid to form a sulfonic acid, after which the aldehyde is added to obtain the condensation product. Occasionally, sodium sulfite may be present during the reaction. According to a preferred embodiment of the present invention, the aqueous dispersion comprises a condensation product of naphthalenesulfonic acid and formaldehyde, commonly referred to as a polycondensate of condensed naphthalenesulfonate.

The amount of condensed sulfonate present in the dispersion can vary within wide limits, depending inter alia on the type of paper stock, and other compounds such as stabilizers, dispersants and sizing agents present in the aqueous dispersion. Typically, the dispersion contains from about 1 to about 20 weight percent condensed sulfonate, suitably from about 1 to about 15 weight percent, preferably from about 2 to about 10 weight percent, based on the size.

The dispersions according to the invention can be anionic or cationic, depending on the amount of starch and/or other additives such as dispersing/stabilizing agents and protective compounds contained in the dispersion. By anionic or cationic dispersions it is understood that the dispersants are anionic or cationic dispersants, ie have an overall anionic or cationic charge. Dispersant (system) refers to any compound present in a dispersion that facilitates dispersion/emulsion formation such as charged polymers (polyelectrolytes) and surfactants. Suitable additives may be any dispersing/stabilizing and protecting agents known in the art such as nonionic polymers; from natural sources, i.e. polysaccharides such as starch, guar gum, cellulose, chitin, chitosan, polysaccharide Cationic, anionic and amphoteric polymers derived from sugars, galactan, dextran, xanthan gum, mannan, dextrin, etc., as well as synthetic organic polymers such as condensation products, e.g. anionic polyurethanes and naphthalene-based Polymeric anionic compounds, such as condensed naphthalenesulfonates, and monomers with anionic groups, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, vinylsulfonic acid, sulfonated styrene and acrylic acid Formed with phosphate esters of hydroxyalkyl methacrylates (optionally copolymerized with nonionic monomers including acrylamide, alkyl acrylates, styrene and acrylonitrile and derivatives of these monomers, vinyl esters, etc.) Other vinyl addition polymers.

Suitably, the dispersion comprises a cellulose reactive sizing agent having a sizing agent content of about 0.1 to about 50 wt%, suitably above 20 wt%. Dispersions containing ketene dimer sizing agents according to the present invention may have a ketene dimer content in the range of 5 to 50 wt%, and preferably about 10 to about 35 wt%. Dispersions or emulsions containing anhydride sizing agents according to the present invention may have an anhydride content in the range of about 0.1 to about 30 wt%, and typically about 1 to about 20 wt%. Dispersions of non-cellulose reactive sizing agents can generally have a sizing agent content of 5 to 50% by weight and preferably 10 to 35% by weight.

By the term "dispersion" is meant both dispersions and emulsions, depending on the physical state of the size.

The dispersions according to the invention can be prepared by a process comprising homogenizing the sizing agent, suitably under pressure, in the presence of an aqueous phase and starch, preferably at a temperature in which the sizing agent is liquid. The resulting aqueous emulsion (droplets containing sizing agent, normally having a size of 0.1-3.5 μm in diameter) is then cooled. Suitable temperatures for ketene dimer sizing agents are about 55°C to 95°C, while anhydrides can be used at lower temperatures.

The dispersion according to the invention can be used in the usual manner as a sizing agent in papermaking using any type of cellulosic fibers, it can be used both for surface sizing and for internal or stock sizing. The term "paper" as used herein is meant to include not only paper, but all types of cellulosic products in sheet and roll form, including, for example, board and paperboard. The paper stock contains cellulose fibers, optionally also inorganic fillers, and generally the content of cellulose fibers is at least 50% by weight, based on the dry paper stock. Examples of common types of inorganic fillers include kaolin, china clay, titanium dioxide, gypsum, talc and natural and synthetic calcium carbonates such as chalk, marble flour and precipitated calcium carbonate.

The amount of sizing added to the paper stock can be 0.01-5 wt%, suitably 0.05-1.0 wt%, based on the dry weight of the cellulose fibers and optional fillers, wherein the amount mainly depends on the pulp or paper stock to be sized quality, the sizing agent used and the level of sizing required.

Furthermore, the dispersions according to the invention are preferably used in the manufacture of paper from paper stocks comprising cellulose fibers and optionally fillers with high electrical conductivity. Typically the conductivity of the paper stock is at least about 0.20 mS/cm, suitably at least 0.5 mS/cm, preferably at least 3.5 mS/cm. Very good sizing was found at conductivity levels above 5.0 mS/cm and even above 7.5 mS/cm. Conductivity can be measured by standard equipment such as the WTW LF539 instrument supplied by Christian Bemer. The aforementioned values are suitably determined by measuring the conductivity of the cellulosic suspension fed to or present in the headbox of the paper machine, or alternatively by measuring the conductivity of the white water obtained from dewatering the suspension. A high conductivity level refers to a high content of salts (electrolytes), where various salts can react with mono-, di-, and polyvalent cations such as alkali metals, such as Na ⁺ and K ⁺ , alkaline earth metals, such as Ca ²⁺ and Mg ²⁺ , Aluminum ions, such as Al ³⁺ , Al(OH) ²⁺ and polyaluminum ions, and mono-, di- and polyvalent anions such as halides, such as Cl ^- , sulfates, such as SO ₄ ^2- and HSO ₄ ^- , carbonates , such as CO ₃ ^2- and HCO ₃ ^- , based on silicate and lower organic acids. The dispersion is especially useful for papermaking from stock having a high content of salts of di- and polyvalent cations, typically a cation content of at least 200 ppm, suitably at least 300 ppm and preferably at least 400 ppm. Salt can be obtained from cellulosic fibers and fillers used to form paper stock, especially in integrated mills where concentrated aqueous fiber suspensions from pulp mills are normally mixed with water to form dilute suspensions suitable for papermaking in paper mills. The salt can also originate from various additives introduced into the paper stock, fresh water supplied to the process, or intentionally added, etc. Furthermore, the salt content is usually higher in processes where white water is recycled in large quantities, which can lead to a large build-up of salt in the water recycled in the process.

The invention is further illustrated in the following examples, however, they are not intended to limit the invention. Parts and % are parts by weight and % by weight, respectively, unless otherwise specified.

Example 1

A preparation containing 8.9% of a technical alkyl ketene dimer, 0.89% of an aromatic substituted cationic starch having a DS of 0.065 and containing benzyl groups, and 0.22% of a condensed naphthalenesulfonate available under the trade name Tamol® Anionic sizing dispersions. The anionic dispersions were added to 30% pine, 30% Bee, 40% eucalyptus in amounts (dry basis) of 0.0125% (Test 1) and 0.0140% (Test 2) based on ketene dimer as shown in Table 1. , and 15% of precipitated CaCO ₃ in the cellulose suspension (dry basis). The conductivity of the suspension was 500 μS/cm. To this suspension was also added a size containing benzyl substituted starch with 0.065 DS (5 kg/ton dry stock) and a condensed naphthalene sulfonate (0.120 kg/metric ton dry stock) obtained under the trade name Tamol® Accelerator.

Table 1 Test No. Anionic sizing dispersion/[kg sizing agent/ton dry paper stock] Cobb 60/[g/m ² ] test 1 0.125 27.0 test 2 0.140 25.5

Example 2

In this example, the same anionic sizing dispersion as in Example 1 was used. In addition, the same benzyl-substituted starches as in Example 1 with 0.065 DS (5 kg/ton of dry stock) and condensed naphthalene sulfonates (0.120 kg/metric ton of dry stock) available under the trade name Tamol® were used. ) sizing accelerator. The anionic sizing dispersion was added to the same cellulose suspension, however, the conductivity of this suspension was 5000 μS/cm instead of 500 μS/cm.

Table 2 Test No. Anionic sizing dispersion/[kg sizing agent/ton dry paper stock] Cobb 60/[g/m ² ] test 1 0.125 33 test 2 0.140 25

Example 3

The sizing performance of cationic sizing according to the prior art was evaluated using the cobb 60 test. The sizing dispersion was prepared by mixing cationic starch without aromatic groups and sulfonated oil with molten AKD having an AKD content of 15% by weight (based on the total dispersion). The papermaking stock contained 85% 30:30:40 pine: birch: eucalyptus kraft pulp and 15% precipitated calcium with addition of _CaCl2 . The stock had a consistency of 2.5 g/l, a pH of 8.1 and a conductivity of 500 μs. The dispersion was used in conjunction with a water retention and dewatering system comprising a phenyl-containing cationic aromatic modified starch having a DSc of 0.065 and a condensed naphthalene sulfonate added separately to the paper stock. Cationic aromatic modified starch was added in an amount of 5 kg/ton, and condensed naphthalenesulfonate was added in an amount of 0.5 kg/ton, based on dry paper stock, respectively.

table 3 Added sizing dispersion/[kg AKD/ton of dry paper stock] Cobb 60/[g/m ² ] 0.122 42

Example 4

In this example, the conditions, that is, the sizing dispersion, the dehydration and water retention system, etc., were the same as in Example 3, however, the conductivity of the paper stock was changed to 5000 μs by adding CaCl ₂ .

Table 4 Added sizing dispersion/[kg AKD/ton of dry paper stock] Cobb 0.122 95

Claims (12)

1. applying glue aqueous dispersion, comprise sizing agent, have the starch and the condensation sulphonic acid ester of aromatic group, wherein the condensation sulphonic acid ester is the aromatic sulfonic acid of being derived by the aromatic compounds in the product that is selected from naphthalene, naphthalene and cresols, diphenyl ether, toluene, cumene, cresols and the phenol and the condensation product of aldehyde, and starch contains the following amylopectin of 95wt%.

2. according to the applying glue aqueous dispersion of claim 1, wherein said starch has following general formula:

Wherein P is the residue of starch; A is the atomic link that comprises C and H atom that N is connected in polysaccharide residue radical, R ₁And R ₂Each is H or alkyl naturally, R ₃Be aromatic hydrocarbyl, n is 2 to 300,000 integer, and X ^-It is anionic counter-ion.

3. according to the applying glue aqueous dispersion of claim 1 or 2, wherein starch contains the following amylopectin of 90wt%.

4. according to the applying glue aqueous dispersion of claim 1 or 2, wherein the condensation sulphonic acid ester is the condensation product of aromatic sulfonic acid and formaldehyde.

5. according to the applying glue aqueous dispersion of claim 1 or 2, wherein the condensation sulphonic acid ester is the condensation product of naphthalene sulfonic acids and formaldehyde.

6. according to the applying glue aqueous dispersion of claim 1 or 2, wherein sizing agent is the cellulose reactive sizing agent.

7. the glue applying method of paper, comprise and to contain sizing agent, contain the starch with aromatic group of the following amylopectin of 95wt% and the applying glue aqueous dispersion of condensation sulphonic acid ester joins in the water slurry that contains cellulose fibre, on papermaking wire-cloth, form and dewatered suspension, wherein suspension has the conductance of 0.5mS/cm at least, and described condensation sulphonic acid ester is the aromatic sulfonic acid of being derived by the aromatic compounds in the product that is selected from naphthalene, naphthalene and cresols, diphenyl ether, toluene, cumene, cresols and the phenol and the condensation product of aldehyde.

8. according to the glue applying method of the paper of claim 7, wherein said starch has following general formula (I):

Wherein P is the residue of starch; A is the atomic link that comprises C and H atom that N is connected in polysaccharide residue radical, R ₁And R ₂Each is H or alkyl naturally, R ₃Be aromatic hydrocarbyl, n is 2 to 300,000 integer, and X ^-Be anionic counter-ion, this starch contains the following amylopectin of 95wt%.

9. according to the glue applying method of the paper of claim 7 or 8, wherein suspension has the conductance of 3.5mS/cm at least.

10. according to the glue applying method of the paper of claim 7 or 8, wherein starch contains the following amylopectin of 90wt%.

11. according to the glue applying method of the paper of claim 7 or 8, wherein the condensation sulphonic acid ester is the condensation product of naphthalene sulfonic acids and formaldehyde.

12. according to the glue applying method of the paper of claim 7 or 8, wherein sizing agent is the cellulose reactive sizing agent.