TWI226915B - Process for sizing paper - Google Patents

Abstract

A process for sizing paper comprising adding to an aqueous suspension containing cellulosic fibres, and optional fillers, an anionic or cationic sizing dispersion, and a sizing promoter comprising a cationic polymer having an aromatic group; and an anionic polymer having an aromatic group selected from step-growth polymers, polysaccharides and naturally occurring aromatic polymers, wherein the sizing dispersion and sizing promoter are added separately to the aqueous suspension.

Description

A7 1226915 V. Description of the invention (/) The present invention relates to a method for sizing paper, which includes adding an anionic or cationic sizing dispersion to a suspension containing cellulose fibers and a selected paste, and containing an aromatic group. Cationic organic polymer and anionic polymer sizing accelerator selected from gradually growing polymers, polysaccharides, and naturally-occurring aromatic polymers, wherein the sizing dispersion and the sizing accelerator are separated To the aqueous suspension. Background Sizing or emulsions of sizing agents are used in papermaking to provide paper and paperboard with improved resistance to wetting and penetration of various liquids. The sizing dispersion is usually added to an aqueous suspension containing cellulose fibers, selected fillers and various additives. The aqueous suspension is fed into an elevated tank to discharge the suspension onto a papermaking web to form a wet fabric of paper there. Suspensions are generally further added with compounds such as starch and particulate materials to facilitate the dehydration of the suspension on the papermaking web. The discharge from the papermaking web, called white water, is usually partly recycled in the papermaking process. Cellulose suspensions contain certain amounts of non-fibrous materials, such as aggregates, charged polymers, sizing agents, and various different charged pollutants, namely anionic residues, electrolytes, and colloidal substances. Non-fibrous materials have an impact on sizing efficiency and generally impair sizing performance. A large amount of charged compounds, such as a high content of salts, in the suspension will gradually make it difficult to sizing the suspension, i.e., to obtain paper with satisfactory sizing properties. Other compounds contained in the suspension that can break the size are various lipophilic wood extracts, which can be derived from recycled fiber and mechanical pulp. Generally, increasing the amount of glue added can improve the size of glue. However, this will lead to higher costs and increase the accumulation of glue in white water. __ _3_ This paper standard (CNS) A4 specification (21 ()) < 297 public love) --- U-. 1 ----------------- order --------- line (Please read the precautions on the back first Fill out this page again) A7 1226915 V. Description of Invention (2). The accumulation of non-fibrous materials and any other ingredients present in the suspension ' will be more pronounced in presses where white water is circulated in large quantities and only a small amount of fresh water is fed into the papermaking process. It is therefore an object of the present invention to further improve the sizing. A further object of the invention is to improve the sizing when applied to a cellulose suspension having a high conductivity and / or a large amount of lipophilic wood extract. Other further purposes will appear below. U.S. Patent No. 6001 166 relates to a dispersion of an aqueous alkyl acetoethylenone containing a cationic starch and an anionic dispersant such as a condensate of lignin sulfate 'naphthalene sulfate and formaldehyde. WO 0023651 relates to anionic and cationic sizing dispersions containing a ketene dimer and at least one anionic dispersant. EP 984101 discloses a sizing composition containing a ketene dimer or acid anhydride and an amino polyresidue selected from N-bis- or tris ((1,2-dicarboxyethoxy) ethyl) amine A complexing agent with phosphonates. U.S. Patent No. 5,972,094 relates to a sizing composition comprising a thermoplastic resin selected from the group consisting of thermoplastic turpentine, thermoplastic hydrocarbon resin, thermoplastic polyamide resin, and thermoplastic wax. U.S. Patent No. 5,595,629 discloses a method for manufacturing paper, which includes forming an aqueous cellulose pulp and adding a cationic polymer and an anionic polymer to the prize solution to increase retention and / or drainage. Anionic polymer is a formaldehyde condensate containing naphthalenesulfonate. Invention The invention according to the scope of the patent application has been found to surprisingly solve problems encountered in applications. More specifically, the present invention relates to paper gluing. 4 wood paper scales are applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 Kg. £ 7 " " ------- (Please read the precautions on the back before (Fill in this page) Φ Order -------- line A7 1226915 V. Method of the invention description (彳), which includes adding anionic or cationic sizing to the suspension containing cellulose fiber and the selected concrete Dispersion liquid, sizing accelerator with aromatic group containing cationic organic polymer with aromatic group, and anionic polymer with aromatic group selected from gradually growing polymer, polysaccharide and naturally-occurring aromatic polymer, in which the size is dispersed The liquid and the sizing accelerator are added separately to the aqueous suspension. The anionic or cationic sizing dispersion is contained in the anionic or cationic sizing dispersion used in the method according to the invention. The sizing agent is suitably any Paper or paperboard can be provided with an increased resistance to wetting and penetration of liquids, such as non-cellulose-reactive agents, including turpentine, such as fortified and / or esterified turpentine ' Derivatives of fatty acids and resin acids, such as fatty amidamines and fatty esters, such as glycerol triesters of natural fatty acids, and / or cellulose-reactive agents. Sizing dispersions are preferred It contains cellulose-reactive I: sizing agent. The cellulose-reactive sizing agent contained in the sizing dispersion can be selected from any cellulose-reactive agent known in the art. It is suitably a sizing agent It is selected from the group consisting of hydrophobic ketene dimers, ketene multimers, acid anhydride 'organic isocyanates, carbamate chlorides and mixtures thereof, preferably ketene dimers and / or acid anhydrides. Suitable for ketene dimerization The system has the following general formula (I), where R1 and R2 represent saturated or unsaturated hydrocarbon groups, usually saturated hydrocarbons, and the hydrocarbon groups suitably have from 8 to 36 carbon atoms. Linear or branched alkyl groups to 20 carbon atoms, such as hexadecyl and octadecyl. The ketene dimer is normally at room temperature, that is, 2YC, and is suitably 20. (: The following can be liquid. Generally, acid anhydride You can borrow the following paper sizes to meet Chinese national standards (CNS) A4 specifications (210 X 297 mm) '(Please read the precautions on the back before filling this page) ____ Order --------- line A7 1226915 B7_ 5. Description of the invention (>) Formula (II) represents its characteristics, wherein R3 and R4 may be the same or different and represent a saturated or unsaturated hydrocarbon group, suitably having from 8 to 30 carbon atoms, or R3 and R4 together with -C-0- The C half can form a 5- to 6-membered ring, and can optionally be further substituted by a smoke group containing up to 30 carbon atoms. Examples of commercially available anhydrides include alkyl and dilute amber Acid anhydrides and especially isostetenyl succinic anhydrides. (1) R—CH = C—CH-R (Π) 〇ⅡII 2 II 4

0_C = 0 R—C—O—C—R Suitable ketene dimers, acid anhydrides, and organic isocyanates include the compounds disclosed in U.S. Patent No. 4,522,686, which are incorporated herein by reference. Examples of suitable amidomethyl chlorides include those disclosed in U.S. Patent No. 3,887,427, which is incorporated herein by reference. The method according to the invention comprises adding to the suspension containing cellulose fibers an anionic or cationic aqueous sizing dispersion, ie a dispersion and / or stabilizer present in the dispersion, which can be referred to as a dispersion system, each of which has Total negative or positive charge. The dispersion system may include any agent that promotes the formation of a dispersion or emulsion, such as a polyelectrolyte, a dispersing and / or stabilizing agent for a surfactant and an electrolyte. The anionic aqueous sizing dispersion may contain a cationic compound, that is, a cationic polyelectrolyte (a cationic or amphoteric polyelectrolyte having a total positive charge) and / or a cationic surfactant, and / or any other cationic compound known to the skilled person, As long as the total charge of the dispersion system can be made negative. On the other hand, the cationic aqueous sizing dispersion may contain anion ______ 6 _ wood paper size Chinese National Standard (CNS) A4 specification (210 X 297 public love) " — " " (Please read the back first Please note this page before filling out this page) ---- · 1111! Line 1226915 a7 ______B7_ V. Description of the Invention (f) \ Sub-compounds, namely anionic polyelectrolyte (anion or rain polyelectrolyte with total negative charge) and / or Anionic surfactants, and / or any other anionic compounds known to the skilled person, so long as the total charge of the dispersion system can be made negative. The negative or positive charge of the sizing dispersion can be determined by the PCS of ZetaMaster S version. According to a preferred embodiment of the present invention, the anionic or cationic sizing dispersion contains a cationic organic polymer having an aromatic group and / or an anionic polymer having an aromatic group. The cationic organic polymer and the anionic polymer may be any of the sizing accelerators described below. The anionic or cationic sizing dispersion added to the suspension may contain from about 0.1 to about 50% by weight of the total weight of the dispersion / emulsion, suitably above 20% by weight of the gum content. The dispersion liquid containing the ketene dimer sizing agent may have a ketene dimer content of 5 to 50% by weight, preferably about 10 to about 35% by weight, based on the total weight of the dispersion. The dispersion or emulsion containing an acid anhydride sizing agent may contain an acid anhydride content of about 0.1 to about 30% by weight, suitably about 1 to about 20% by weight, based on the total weight of the dispersion / emulsion. The dispersion containing a non-cellulose-reactive sizing agent suitably has a sizing agent content of 5 to 50% by weight, preferably 10 to 35% by weight. The amount of the sizing agent to be added to the aqueous suspension containing cellulose fibers may be 0.01 to 5% by weight, suitably 0.05 to 1.0% by weight, based on the dry weight of the cellulose fibers and the selected materials. The dosage is mainly According to the quality of the pulp or paper to be glued, the size and size of the glue used. According to the present invention, the anionic or cationic sizing dispersion contains and has (Please read the precautions on the back before filling this page) -------- Order --------- Line ---- 7 __ This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) A7 1226915 V. Description of the invention (6) Aromatic cationic organic polymers and polymers, polysaccharides and natural The aromatic polymer selected as the anionic polymer with a sizing accelerator is separately added to the aqueous suspension. Although the sizing dispersion may contain the same polymers as those contained in the sizing accelerator, the sizing can only be observed when the sizing accelerator and the sizing dispersion are added separately to the cellulose suspension. Significant improvement. Separate addition means that the sizing dispersion and sizing accelerator of any polymer that may contain a sizing accelerator are added to the cellulose suspension (thin raw material) at different locations or essentially at the same location But at different times. In addition, the cationic organic polymer and the anionic polymer forming the sizing accelerator are also suitably added separately. The anionic polymer is preferably added to the suspension after sizing the dispersion and the cationic organic polymer. According to a preferred embodiment of the present invention, the method of sizing paper comprises adding an anionic or cationic sizing dispersion to a suspension containing cellulose fibers and a selected paste, and containing a solution containing cationic polysaccharide or cationic ethylene. A cationic organic polymer with an aromatic group selected from the base addition polymer and a sizing accelerator selected from a gradually growing polymer, a polysaccharide, and a naturally-occurring aromatic polymer. The sizing dispersion and the sizing accelerator are added separately to the aqueous suspension. The cationic polymer is preferably selected from cationic polysaccharides having the general structural formula (I):

Ri ® P— (一 A—N—R2) n R3 8 Wood paper size is applicable to Chinese National Standard (CNS) A4 (210 x 297 mm) (Please read the notes on the back before filling this page) Φ Order- -------- Line 1226915 Fantasy _ V. Description of the invention (7) where P is a polysaccharide residue; A is an atomic chain containing C and plutonium atoms that links N to the polysaccharide residue, and the heart and R2 Each is fluorene or a hydrocarbon group, R3 is an aromatic hydrocarbon group, η is an integer from 2 to 300,000, and X- is an anion counter ion; and / or is represented by polymerizing a cationic monomer or containing a general formula (II) Vinyl addition polymer obtained from monomer mixture of cationic monomers: R2 (Π)

-Q (Please read the notes on the back before filling this page) CH2 = C—Ri O C-Αι-B]-

Rs where 1 is H or CH3; 112 and R3 are each an alkyl group having 1 to 3 carbon atoms, Ai is 0 or NH, and Bi is an olefin group or a hydroxypropene group having 2 to 8 carbon atoms, Q is an aromatic group-containing substituent, and X_ is an anion counter ion. A cationic polymer having an aromatic group is more preferably selected from a cationic polysaccharide having a general structural formula ⑴:

Rl (1), I + X · P — (― Α-Ν—R2) n R3 where P is a polysaccharide residue; a is an atomic chain containing C and Η atoms that links N to the polysaccharide residue, I And 112 each is a fluorene or a hydrocarbon group, I is an aromatic hydrocarbon group, η is an integer from 2 to 300,000, and X- is an anion counter ion. Sizing accelerator, a cationic organic polymer with a certain aroma. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 1226915. 5. Description of the invention (?) The cationic organic polymer having one or more aromatic groups may be derived from natural or synthetic sources, and may be linear, branched, or cross-linked. The cationic polymer is preferably water-soluble or water-dispersible. Examples of suitable cationic polymers include cationic polysaccharides such as starch, guar, cellulose, chitin, chitosan, polysaccharides, galactan, polydextrose, gluten Resin, pectin, mannan, dextrin, preferably starch and guar, suitable starches include potato, maize, wheat, cassava flour, rice, maize, barley, etc .; cationic synthetic organic polymers For example, cationic chain-growth polymers, such as cationic vinyl addition polymers such as acrylic acid, acrylamide, and vinylamine-based polymers, and cations such as cationic polyurethanes grow progressively. Of polymers. Suitably, a cationic organic polymer having an aromatic group selected from a polysaccharide, that is, starch and a cationic vinyl addition polymer such as an acrylamide-based polymer is particularly preferred. 0 The aroma of the cationic organic polymer The radical may be present on the backbone (backbone) of the polymer or on a substituent attached to the backbone of the polymer, preferably on the substituent. Examples of suitable aromatic groups include aromatic groups, aralkyl groups and alkaryl groups, such as phenyl, phenylene, naphthyl, benzyl, benzyl and phenethyl, preferably benzyl; containing Aromatic (aromatic) groups of nitrogen, that is, pyridine gun and quinone gun, and derivatives of these groups. Examples of charged cations that may be present in the cationic polymer and in the monomers used to prepare the cationic polymer include quaternary ammonium groups, tertiary amine groups, and acid addition salts thereof. According to a preferred embodiment, a cationic organic polymer having an aromatic group __ 10 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) ^ Γ · 1 ·· — in emat It n «m« ϋ M ^ 鳒 μ ·· an ·· w ·· μμτ Xikou line A7 B7 1226915 V. Description of the invention (?) The compound is selected from cationic polysaccharides. The aromatic group of the polysaccharide may be attached to a heteroatom present in the polysaccharide such as nitrogen or oxygen, and the heteroatom may optionally be charged, for example, when it is nitrogen. Aromatic groups can also be attached to groups containing heteroatoms, such as amidoamines, esters or ethers, which groups can be attached to the backbone (backbone) of polysaccharides, for example via an atomic chain. Suitable examples of aromatic groups and groups contained in aromatic groups include aromatic groups and aromatic groups such as phenyl, phenylene, naphthyl, phenylene, xylylene, Tyl and benzene Ethyl; nitrogen-containing aromatic (aromatic) groups, such as pyridine D and quinoline, and derivatives of these groups, in which one or more substituents attached to the aromatic group may be selected from Hydroxyl groups are, for example, halides of chlorides, nitro groups, and hydrocarbon groups having 1 to 4 carbon atoms. The cationic organic polymer is preferably selected from the cationic polysaccharide having the general structural formula (I):

Ri ① (Ux 'P — (-A—N-R2) n R3 where P is the residue of polysaccharides; A is a group that attaches N to the residue of polysaccharides, suitably containing C and Η atoms and selected A chain of atoms of 0 and / or N atoms, usually an olefin-based group having from 2 to 18 and suitably 2 to 8 carbon atoms, optionally by one or more heteroatoms such as 0 or N Interruption or substitution, such as an alkoxy group or a hydroxypropenyl group (-CH2_CH (OH) -CH2-); each of K and Ri is Η or preferably a hydrocarbon group, suitably having 1 to 3 Carbon atom, suitably 1 or 11 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) Φ Order ------- --Line A7 1226915 V. Description of the invention (/ ο) An alkyl group of 2 carbon atoms; R3 is an aromatic hydrocarbon group including an aralkyl group, such as a fluorenyl group and a phenethyl group; η is from about 2 To about 300,000, suitably an integer of 5 to 200,000 and preferably 6 to 125,000, or additionally Ri, R and R3 together with N to form an aromatic group containing from 5 to 12 carbon atoms; and X is anion The counter ion of ions is usually a halide such as chloride. Aromatically modified cationic polysaccharides can have a wide range of degrees of substitution; the degree of cationic substitution (DSC) can be from 0.01 to 0.5, suitably from 0.02 to 0.3 , Preferably from 0.025 to 0.2, the degree of aromatic substitution (DSA0 may be from 0.01 to 0.5, suitably from 0.02 to 0.3, preferably from 0.025 to 0.2, and the degree of anionic substitution (DSA) may be from 0 to 0.2, suitably from 0 to 0.1, preferably from 0 to 0.05. Polysaccharides can be obtained by passing the polysaccharides in a known manner using cations of one or more agents containing one or more cationic groups and / or aromatic groups. Aromatic modification to prepare, such as reacting polysaccharides with pharmaceutical agents in the presence of alkaline substances such as alkali metal or alkaline earth metal hydroxides. Polysaccharides to be modified by cations and aromatics can be nonionic, anionic Amphoteric or cationic. Suitable modifiers include non-ionic agents, such as aralkyl halides, such as benzyl chloride and benzyl bromide; epichlorohydrin and at least one substituent containing as defined above Reaction products of aromatic dialkylamines, including 3-dialkylamine-1,2-epoxypropanes; and cationic agents, such as epichlorohydrin and having at least one substituent containing as defined above Products of aromatic tertiary amines, including alkaryldialkylamines, such as dimethylbenzylamine; aromatic amines, such as eupridine and quinoline. Suitable types of this type ____12 _ P The Zhang scale is applicable to the Chinese National Standard (CNS) A4 specification (21 ^ 297 Public Love 1 " " U --- L ----------------- Order ----- -----— ^^ 1 (Please read the precautions on the back before filling out this page) A7 1226915 ______ ^ B7____ 5. Description of the invention (丨 丨) The ionic pharmaceuticals include 2,3-epoxypropyltrioxane Halogenated amines and halohydroxypropyltrialkyl halide amines, such as N- (3-chloro-2-hydroxypropyl) -N- (hydrophobic alkyl) -N, N-di (low carbon Alkyl) ammonium chloride and N-glycidyl-N- (hydrophobic alkyl) -N, N-di (lower alkyl) ammonium chloride, where the aromatic group is as defined previously, especially octyl And decyl and dodecyl, and the lower alkyl is methyl or ethyl; and halohydroxypropyl-N, N-dioxane -N-alkylaryl ammonium amine and N-glycidyl-N- (alkaryl) -N, N-dialkyl amine chloride, such as N- (3-chloro-2-hydroxypropyl) ) -N- (alkaryl) -N, N-di (lower alkyl) ammonium chloride, in which the alkylaryl and lower alkyl groups are as previously defined, especially N-0-chloro- 2-hydroxypropyl) -N-fluorenyl-N, N-dimethylamine chloride; and (3-chloro-2-hydroxypropyl) pyridine chromium chloride. In general, when a nonionic aromatic agent is used, the polysaccharide may be provided with a cationic property appropriately before or after the hydrophobic modification by using any of cationic agents known in the art. Examples of suitable cationic and / or aromatic modifiers, aromatic-modified polysaccharides, and methods for preparing the same include US Patent Nos. 4,687,519 and 5,463,127; International Patent Application WO 94/24169, European Patent Application No. No. 189 935; starch with SP Patel, RG Patel, and VS Patel, 41 (1989), Vol. 5, pp. 192-196, the teachings of which are hereby incorporated by reference. According to yet another preferred embodiment, the cationic organic polymer is a homopolymer prepared from one or more monomers containing at least one monomer having an aromatic group, suitably an ethylene unsaturated monomer, and In the copolymer. Synthetic polymers can be branched or branched. Synthetic polymer # 香 基 圑 can be present on the polymer backbone or preferably it is a pendant polymer on the backbone of the delirium polymer or extends from the polymer backbone _ or _____ 13_ ^ P Zhang Zhang National Standard (CNS) A4 Specification (210 X 29Γmm) '(Please read the precautions on the back before filling this page) -------- Order -------- * Line 1226915 A7 B7 1 V. Description of the invention (A) is on the pendant group attached to or extended from the polymer trunk. Suitable aromatic (aromatic) group systems include phenyl, Optionally substituted, phenylene, optionally substituted, and naphthyl, optionally substituted, such as groups having the general formula, -C6H4-, -C6H3-, and -c6H2-, such as the form Phenylene (-c6H4-), xylylene (-ch2-c6h4-ch2-), phenyl (-c6h5), benzyl (-CH2-C6H5), phenethyl (-CH2CH2-C6H5), And substituted phenyl (for example, -c6h4-y, -c6h3y2, and -c6h2y3), wherein one or more of the substituents (Y) attached to the phenyl ring may be selected from a hydroxyl group, such as a halide of chloride, nitrate base Hydrocarbon group having from 1 to 4 carbon atoms. The cationic polymer is preferably a vinyl addition polymer. As used herein, the term `` vinyl addition polymer '' refers to a polymer prepared by the addition of one or more vinyl monomers or ethylene unsaturated monomers, and includes, for example, acrylamide-based polymers And acrylic based monomers. The cationic polymer is suitably selected from a cationic vinyl addition polymer obtained by polymerization of a cationic monomer or a monomer mixture containing a cationic monomer represented by the general formula (Π): CH2 = C—Ri r2 (Π )

0-:-C-Α \ -Bj-N-QX r3 whose center is fluorene or CH3; each of R2 and R3 is n or, preferably a hydrocarbon group having from 1 to 3 carbon atoms, usually 1 to 2 Carbon atoms; At is 0 or ΝΗ; Bi is from 2 to 8 carbon atoms, preferably from 2 14 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ^ --- -------------- Order · -------- line (please read the precautions on the back before filling this page) A7 1226915 V. Description of Invention (ί)) to 4 Alkene group of 1 carbon atom, or hydroxypropenyl group; Q is a substituent containing an aromatic group, preferably a phenyl group or a substituted phenyl group, which can be usually passed through having 1 to 3 carbon atoms, preferably 1 to An olefin group of 2 carbon atoms is connected to the nitrogen, and Q is preferably a benzyl group (-CH2-C6H5); and 1 is an anion counter ion, which is generally similar to a chloride halide. Examples of suitable monomers represented by the general formula (Π) include treatment with benzyl chloride such as dimethylaminoethyl [meth] acrylate, diethylaminoethyl [meth] acrylate, and [formaldehyde] [Meth] acrylic acid dimethylaminohydroxypropyl acrylate [meth] acrylic acid dialkylaminoalkyl alkyl esters and, for example, dimethylaminoethyl [meth] acrylamidoamine, diethylaminoethyl [Methyl] acrylamide, dimethylaminopropyl [meth] acrylamine, and dialkylaminoalkyl [methyl] with diethylaminopropyl [meth] acrylamine Tertiary monomer obtained from acrylamide. Preferred cationic monosystems of the general formula (Π) include quaternary dimethylaminoethyl benzyl chloride quaternary salt and dimethylaminoethyl methacrylate benzyl chloride quaternary salt. The cationic vinyl addition (synthetic cationic) polymer may be a homopolymer prepared from a cationic monomer having an aromatic group or a polymer containing a cationic monomer having an aromatic group and one or more copolymerizable monomers. Copolymer prepared from monomer mixture. Suitable copolymerizable non-ionic monosystems include monomers represented by the general formula (III): CH2 == C R4 Rs 15 (ΠΙ) 〇 C eight 2-B2- ^ R6 where R4 is η or CH3; Each of R5 and 1 is a fluorene or a hydrocarbon group, suitably having from 1 to 6, suitably from 1 to 4, and usually from 1 15 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public Li)! --- Lj ----------------- Order --------- (Please read the notes on the back before filling out this page) 1226915 V. Description of the invention (a) (Please read the notes on the back before filling out this page) to an alkyl group of 2 carbon atoms; person 2 is 0 or NH; B2 is from 2 to 8 carbon atoms, suitably from 2 to An alkene group of 4 carbon atoms, or hydroxypropene, or alternatively neither of A and B, thereby having a single bond between C and N (0 = C-NR5R6). Suitable examples of this type of copolymerizable monomer include [meth] acrylamide; for example, N-alkyl [meth] acrylamide and N, N-dialkyl [meth] acrylamide Acrylamide-based monomers are, for example, N-n-propylacrylamide, N-isopropyl [meth] acrylamide, N-n-butyl [meth] acrylamide, N- Isobutyl [meth] acrylamide and N-third butyl [meth] acrylamide; and dialkylaminoalkyl [meth] acrylamide, such as dimethylaminoethyl [Methyl] acrylamide, diethylaminoethyl [meth] acrylamine, dimethylaminopropyl [meth] acrylamine and diethylaminopropyl [meth] propylene Ammonium amine; acrylic-based monomers such as dialkylaminoalkyl [meth] acrylate, such as dimethylaminoethyl [meth] acrylate, diethylamine [meth] acrylate Methyl ethyl, tert-butyl methyl amino ethyl [meth] acrylate and dimethyl amino hydroxy propyl acrylate; and ethylene fluorene, such as N-ethylene methylamine and N-ethylene acetamide. The preferred copolymerizable nonionic monosystem includes acrylamide and methacrylamide, that is, [meth] acrylamide, and the main polymer is preferably a polymer based on acrylamide. Suitable copolymerizable cationic monosystems include monomers represented by general formula (IV):

0-- C-A3-B3-N-Ri〇X R9 16 This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 1226915 a7 _ B7____ 5. Description of the invention (A) Where R7 is Η Or CH3; each of R8, R9, and Rio is Η or preferably a hydrocarbon group, suitably an alkyl group having from 1 to 3 carbon atoms, usually 1 to 2 carbon atoms; A3 is 0 or ΝΗ B3 is an alkene group, or a hydroxypropenyl group, from 2 to 4 carbon atoms, suitably from 2 to 4 carbon atoms, and X 'is an anion counter ion, usually methyl sulfate or a chloride halide. Examples of suitable cationic copolymerizable monomers include acid addition salts and the dialkylaminoalkyl [meth] acrylates and dialkylaminoalkyl [meth] acrylamides mentioned above. The quaternary ammonium salt 'is usually prepared by using acids such as HC1, H2S04, etc. or a quaternizing agent such as methyl chloride, dimethyl sulfate, and diallyl dimethyl ammonium chloride. Preferred copolymerizable cationic monosystems include quaternary dimethylaminoethyl [meth] acrylate methyl chloride and diallyldimethylammonium chloride. Copolymerizable anionic monomers such as acrylic acid, methacrylic acid, various sulfonated vinyl addition monomers, etc. can also be used, preferably in a small amount. The cationic vinyl addition polymer may contain, from 1 to 99 mole%, preferably from 2 to 50 mole%, and preferably from 5 to 20 mole% of a cationic monomer having an aromatic group. It is preferably represented by general formula (II), and from 99 to 1 mole%, preferably from 98 to 50 mole%, and preferably from 95 to 80 mole%, and the other preferably contains propylene. A monomer mixture of copolymerizable monomers of amine or methacrylamide ([meth] acrylamide) is prepared, the monomer mixture suitably contains from 98 to 50 mole% and preferably from 95 The total of [meth] acrylamide to 80 mol% is 100. The cationic polymer may also be selected from polymers prepared from a condensation reaction of one or more monomers having an aromatic group. Examples of this monomer include two different 17 *-^ ----------------- order ---------- line (Please read the precautions on the back before (Fill in this page) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) A7 1226915 V. Description of the invention () Toluene cyanate, bisphenol A, phthalic acid, phthalic anhydride, etc. It can be used in the preparation of cationic polyurethane, cationic polyamine, etc. In addition, the cationic polymer can be an aromatic modified polymer by using an agent containing an aromatic group, and this type is appropriately modified Agents include fluorenyl chloride, fluorenyl bromide, N- (3-chlorohydroxypropyl) -N-benzyl-N, N-dimethylammonium chloride, and N- (3-chloro-2- Hydroxypropyl) pyridine chloride. Suitable polymers for this aroma modification include vinyl addition polymers. If the polymer contains a tertiary nitrogen that can be modified by quaternization with a pharmaceutical agent, the use of this agent usually results in the polymer being cationic. In addition, the polymer to be aromatized can be cationic, for example, it is a cationic vinyl addition polymer. Generally, the charge density of the vinyl addition polymer to the dry polymer is from 0.1 to 6.0 meqv / g. In the range, it is preferably from 0.2 to 4.0 and more preferably from 0.5 to 3.0. The weight average molecular weight of the synthetic polymer is usually at least about 50,000, suitably at about 1,000,000, and preferably above about 2.000.000. The upper limit is unimportant; it can be about 50,000,000, usually 30,000,000 and suitably 25,000,000. Anionic polymer with aromatic group of sizing accelerator Do not include the anionic polymer with aromatic group in the glue accelerator of the present invention, which is selected from gradually growing polymers, polysaccharides and naturally occurring aromatic polymers . The term "gradually growing polymer" as used herein refers to a polymer obtained by gradually growing polymerization, and also refers to step_reactive polymer and step-reactive polymerization. The anionic polymer preferably has 18 copies. Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) ^ I-(Please read the precautions on the back before filling this page) # Order --------- Line A7 1226915 5 Description of the Invention (β) Aromatic group and the book is an anionic polymer that does not contain melamine or a derivative. The anionic polymer is suitably an aromatic polymer and the book is an anionic polymer that does not contain a melamine or a derivative and is not anionic Polystyrene sulfonate. Anionic polymers can be selected from gradually growing polymers and naturally occurring aromatic polymers. Anionic polymers according to the present invention can be linear, branched or crosslinked. Anionic polymers are generally It is water-soluble or water-dispersible. The anionic polymer is preferably organic. The anionic aromatic polymer is preferably a polymer and example of a condensed naphthalenesulfonate type such as a condensed naphthalenesulfonate. It is a modified lignin polymer of lignin sulfonate. The aromatic group of the anionic polymer can exist on the polymer backbone or on the substituent attached to the polymer backbone (main chain). Suitable aromatic group Examples include aromatic, aralkyl, and alkaryl groups and their derivatives, such as phenyl, tolyl, naphthyl, phenylene, xylylene, benzyl, phenethyl, and the like. Derivatives. Examples of anionic charged groups that may be present in the anionic polymer and in the monomers used to prepare the anionic polymer include groups that are negatively charged and negatively charged when dissolved or dispersed in water. Acid groups' groups here are collectively referred to as anionic groups, such as phosphate, phosphonate, sulfate, sulfuric acid, sulfonate, carboxylic acid, ammonium acid, alkoxide and group, that is, hydroxy-substituted phenyl and Naphthyl. The negatively charged groups are usually metal test, alkaline earth metal or ammonia salts. Examples of suitable anionic gradual growth polymerization products according to the present invention include condensation polymers, ie, gradual growth condensation polymerization cooperation The obtained polymer is, for example, a polymer of aldehydes such as formaldehyde and one or more aromatic compounds containing one or more anionic groups, especially a condensation type of naphthalene sulfonate. _____ 19 paper ruler ^ China National standards ((: milk from 4 specifications (21〇) < 297) ~ (Please read the precautions on the back before filling out this page) t Order --------- line · A7 1226915 ____B7______ V. Invention Description (and other optional condensates of comonomers that can be used, for example, in condensation polymerization of urea. Examples of suitable aromatic compounds containing anionic groups are compounds containing phenol and naphthol, such as phenol , Naphthalene powder, resorcinol and its derivatives, aromatic hydroxy acids and their salts, such as phenol, phenol, naphthalene and naphthol and their salts, usually sulfuric acid and sulfonate, such as benzene sulfuric acid and Sulfonate, xylene sulfuric acid and sulfonate, naphthalene sulfuric acid and sulfonate, phenol sulfuric acid and sulfonate. Examples of further suitable anionic gradual-growth polymerization products according to the present invention include addition polymers, ie polymers obtained by gradual-growth addition polymerization, such as those which can be obtained from aromatic isocyanates and / or aromatic alcohols. Anionic polyurethanes prepared from similar monomer mixtures. Examples of suitable aromatic isocyanates include diisocyanates, such as toluene-2,4- and 2,6-diisocyanate and diphenylmethane-4,4'-diisocyanate. Examples of suitable aromatic alcohols include glycols, that is, diols, such as bisphenol A, phenyl diethanolamine, triethylene terephthalate, and trimethylol propyl monoterephthalate. . Monohydroxyaromatic alcohols such as phenol and its derivatives can also be used. The monomer mixture may also contain non-aromatic isocyanates and / or alcohols, usually diisocyanates and glycols, such as any producer known to be useful in polyurethanes. Examples of suitable monomers containing anionic groups include triols such as trimethylolethane, trimethylolpropane and glycerol, and dicarboxylic acids such as succinic acid and anhydride, terephthalic acid and anhydride, or The monoester reaction products of the anhydrides thereof are, for example, glyceryl monosuccinate, triglyceryl monoterephthalate, trimethylolpropyl monosuccinate, trimethylolpropyl monoterephthalate, N , N-bis- (hydroxyethyl) _glycine: _ 20 ______ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ut nt «n ϋ ϋ ϋ nnnn · nnn ϋ n ϋ n One-port VI n I flu nnnn I (Please read the notes on the back before filling this page) 1226915 A7 ____ B7___ V. Description of the invention (θ), di- (hydroxymethyl) propionic acid, N, N-bis -(Hydroxyethyl) -2-amineethanesulfonic acid, etc., which is selected and usually reacts with alkalis, such as alkali metal and alkaline earth metal hydroxides, such as sodium oxide, ammonia or amine, such as tris Ethylamine, thereby forming an alkali metal, alkaline earth or ammonium counter ion. Examples of suitable anionic chain-growth polymerization products according to the present invention include those obtained from a mixture of vinyl or ethylene unsaturated monomers containing at least one monomer having an aromatic group and at least one monomer having an anionic group. Anionic vinyl addition polymers are usually copolymerized with non-ionic monomers such as acrylic acid and acrylamide-based monomers. Examples of suitable anionic monomers include [meth] acrylic acid and para-ethylene Hydrazone [hydroxystyrene]. Examples of suitable anionic polysaccharides include starch, guar gum, cellulose, chitin, chitosan, polysaccharides, galactans, polydextrose, gum resin, pectin, manna Polysaccharides and dextrin are preferably starch, guar gum and cellulose derivatives. Suitable starches include potato, maize, wheat, cassava flour, rice, wax maize and barley, preferably potato. Anionic groups in polysaccharides can be natural and / or chemically treated for ingestion. The aromatic groups in the polysaccharides can be fed by chemical methods known in the art. Examples of suitable (modified) naturally occurring aromatic anionic polymers of the present invention include kraft lignin, such as modified lignin polymers, such as lignin compounds copolymerized with formaldehyde and sulfonated lignin For example, it is lignin sulfonate and tannin extract, which are naturally occurring polyphenolic substances that appear in organic extracts of bark of certain wood ingredients. 21 ____ This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- Order ------- --Line · 1226915 a? ____ B7 ___ 5. Description of the invention (〆) Anionic polymers with aromatic groups are appropriately selected from gradually growing polymers, polysaccharides, and naturally occurring aromatic polymers. Polymers in the form of condensed naphthalene sulfonates such as condensed Chai sulfonates and modified lignin polymers such as lignin sulfonates are preferred. The weight-average molecular weight of the anionic polymer can vary within wide limits, particularly depending on the type of polymer used, and typically it is at least about 500, preferably above about 2,000 and preferably above about 5,000 . The upper limit is not important; it may be about 200,000,000, usually 150,000,000, preferably 100,000,000, and preferably 1,000,000. Anionic polymers can have a wide range of anionic substitution degrees (DSA), particularly depending on the type of polymer used; DSA is usually from 0.01 to 2.0, preferably from 0.02 to 1.8 and preferably from 0.025 to 1.5 And the degree of aromatic substitution (DSQ) may be from 0.001 to 1.0, usually from 0.01 to 0.8, suitably from 0.02 to 0.7, and preferably from 0.025 to 0.5. In the case where the anionic polymer contains a cationic group, the degree of cationic substitution (DSc) may be, for example, from 0 to 0.2, suitably from 0 to 0.1, and preferably from 0 to 0.05. The anionic polymer has a total Negative charge. Generally, the negative charge density of the anionic polymer to the dry polymer ranges from 0.1 to 6.0 meqv / g, suitably from 0.5 to 5.0 and preferably from 1.0 to 4.0. According to another preferred embodiment of the present invention, the sizing accelerator contains a cationic organic polymer selected from cationic polysaccharides having the structural formula (I): 22 (Please read the precautions on the back before filling this page) VI ϋ l ·-i ^ w -------- Order · ----, — 丨 The paper size of the paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) A7 1226915 _B7 V. Description of the invention (W) (Please read the notes on the back before filling this page) P — (— A—N—R2) n R3 where P is the residue of polysaccharides; A is the content that links N to the residue of polysaccharides A chain of atoms of C and Η, 1 and 每 are each Η or a hydrocarbon group, R3 is an aromatic hydrocarbon group, η is an integer from 2 to 300,000, and X_ is an anion counter ion; or by polymerizing a cationic monomer or Vinyl addition polymer obtained from a monomer mixture containing a cationic monomer represented by general formula (II): CH2 = C—R! R, 2 ⑻ 0 = C—Αι——B! —— N1—Q x " R3 where 1 is H or CH3; 112 and R3 are each an alkyl group having 1 to 3 carbon atoms, Ai is 0 or NH, and Bi is an alkyl group having 2 to 8 carbon atoms Hydrocarbon group or hydroxypropenyl group, Q is a substituent containing an aromatic group, and is an anion counter ion; and anionic polymers with aromatic groups are gradually growing polymers, polysaccharides, and naturally occurring aromatic polymers. Elected. According to another preferred embodiment of the present invention, the sizing accelerator contains a cationic organic polymer selected from cationic polysaccharides having the structural formula (I): 23 This paper size is applicable to the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) A7 1226915 ___B7 5. Description of the Invention (P)

R3 where P is a polysaccharide residue; A is an atomic chain containing C and fluorene atoms linking N to the polysaccharide residue, R! And R2 are each fluorene or a hydrocarbon group, R3 is an aromatic hydrocarbon group, and η is from 2 An integer of up to 300,000, and X · is an anion counter ion; and an anionic polymer having an aromatic group is selected from gradually growing polymers, polysaccharides, and naturally-occurring aromatic polymers. The sizing accelerator-containing cationic organic polymer having an aromatic group and the anionic polymer having an aromatic group may be added to the aqueous suspension (raw material) in any order separate from the addition of the sizing dispersion and the amount thereof may be particularly Variations in a wide range related to the types of raw materials, salt content, salt types, seasoning content, seasoning type, adding point, etc. Generally, the polymer is added in an amount that gives better gelatinity than when it is not added. Usually, the cationic polymer is added to the raw material before the anionic polymer is added. The cationic polymer is usually made up of at least the dry raw material. It is added in an amount of 0.001% by weight, usually at least 0.005%, but the upper limit is usually 3% and preferably 2.0% by weight. The anionic polymer is usually added in an amount of at least 0.0001% by weight, usually at least 0.0005, of the dry raw material, but the upper limit is usually 3% and preferably 1.5% by weight. In addition to cationic organic polymers and anionic polymers, the sizing accelerator may also contain other compounds that can improve the sizing efficiency, such as anionic particulate materials, such as silica-based particles and montmorillonite_______24 Use Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----- (Please read the precautions on the back before filling this page) · —— Order --------- line 1226915 A7 -----B7 _ ^ ___ 15. Description of the invention (W) clay, low molecular weight cationic organic polymers, such as alum, aluminates, aluminum chlorides, aluminum nitrates, and aluminum compounds such as polyaluminum Chlorides, polyaluminum compounds of polyaluminum sulfate, polyaluminum compounds containing both chloride and sulfate ions, polyaluminosilicate-sulfate and mixtures thereof, anionic vinyl addition polymers and combinations thereof. The method of the present invention is preferably used for the manufacture of papers containing cellulose fibers and a suspension having a high conductivity, which is selected from the group of materials. Generally, the conductivity of the raw material is at least 0.20 microSiemens / cm, suitably at least 0.5 microSiemens / cm, and preferably at least 3.5 microSiemens / cm. Very good sizing results can be observed at a degree of conductivity above 5.0 microSiemens / cm and even above 7.5 microSiemens / cm. Conductivity can be measured with standard equipment, such as the WTW LF 539 instrument supplied by Christian Berner. The aforementioned data is preferably measured by measuring the conductivity of the cellulose suspension fed into or present in the upper box of the paper machine, or alternatively by measuring the conductivity of the white water obtained by dewatering the suspension. Coefficient to decide. High degree of conductivity refers to high salt (electrolyte) content, where various salts can be based on mono, di and polyvalent cations, such as alkali metals, such as Na + and K +, such as alkaline earth metals, such as Ca2 + and Mg2 + Aluminum ions, such as ai3 +, A1 (0H) 2+, and polyaluminum ions, and mono-, di-, and polyvalent anions, such as halides, such as cr, such as sulfate, such as S042 · and HS04 ·, carbonic acid Roots, such as C032 · and HC (V 'silicate and low-carbon organic acids. The present invention is particularly useful for making paper from raw materials having a high content of bis and polyvalent cation salts, and usually The cation content is at least 200 ppm and suitably at least 300 ppm. _ 25 This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) • · I nnnn ϋ n I nnn ϋ n In mmtw I · 1 II n in n 1226915 A7 _____ __ 5. Description of the invention (>) and preferably at least 400 ppm. Salts can be derived from cellulose used to form raw materials Fibers and aggregates, especially during integration In the machine, the concentrated aqueous fiber suspension from the pulp press is usually mixed with water to form a diluted suspension suitable for the manufacture of paper for the pulp press. Salt can also come from various different feed materials. Additives come from the fresh feed water supplied to the process, or are intentionally added, etc. Furthermore, the salt content in the method of prolonged circulation of white water is usually high, which can cause the salt in the water to be recycled in the method to be equivalent. The present invention further includes a papermaking method for large-scale recovery (recycling) of white water, that is, a high degree of whitewater use, such as from 0 to 30 tons of fresh water per metric ton of dry paper, and generally per metric ton of dry paper. Use less than 20, preferably less than 15, preferably less than 10, and especially less than 5 tons of fresh water. In the process, the white water recirculation is preferably obtained by combining white water with cellulose fibers and And / or the selected materials are mixed to form a suspension to be glued: preferably, the suspension contains white water and cellulose fibers, It can be mixed with the suspension of the selected materials. Of course, the additives traditionally used in papermaking can of course also be used in combination with the polymer according to the invention, such as additional dry strengthening agents, wet strengthening agents, cellulose suspensions, Or the raw materials can also contain traditional types of mineral materials, such as kaolin, magnetic clay, titanium dioxide, gypsum, talc and natural and synthetic calcium carbonate, such as chalk, earth marble, and deposited calcium carbonate. The method of the present invention uses Manufacture of paper. The term "paper_ 26 ___" used here is the standard of Chinese paper (CNS) A4 (21〇x 297 mm). (Please read the precautions on the back before filling this page) · n I n I nn ϋ. Ϋ n I n line 1226915 B7 V. Description of invention (meaning) ”Of course, it does not include paper and its manufacture, but also other sheet or fabric-like products, such as board and Cardboard and its manufacture. This method can be used on papermaking from different types of suspensions containing cellulose fibers, and the suspensions preferably contain at least 25% by weight and preferably at least 50% by weight of fibers based on dry matter. The fibers of the suspension can be based on mechanical pulps such as chemical pulps such as sulfates, sulfites and organosols, such as thermomechanical pulps, chemical-thermomechanical pulps, scouring pulps and ground wood pulps from hardwood and softwood It can also be based on recycled fibers, optionally from deinked pulp, and mixtures thereof. The invention is particularly applicable to the manufacture of paper from suspensions based on pulp containing recycled fibers and deinked pulp, and the content of cellulose fibers from this source can be as high as 100%, suitably from 20% to 100%. The present invention is further illustrated by the following examples, but it is not limited to these examples. Unless otherwise stated, parts and% refer to weight fraction and weight%, respectively. In all the examples below, the sizing dispersion and the sizing accelerator are separately added to the cellulose suspension. Further, in the case where the accelerator contains more than one polymer having an aromatic group, these polymers are added to the suspension separately from each other and the dispersion. The sizing properties of the method of Example 1 were evaluated by using a cobb 60 test. An anionic sizing dispersion containing an alkylketene dimer, a condensed naphthalenesulfonate and bis (hydrogenated tallow) dimethylamine chloride was prepared. The sizing dispersion has a AKD content of 30% and contains 2% based on AKD (hydrogenated beast! ____ 27______) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) I ϋ nninmn I i I n -n ϋ nnn a ”· nn I nnn I (Please read the notes on the back before filling this page) 1226915 A7 B7 V. Description of the invention (A) Fat) Condensation of dimethylamine chloride and 6% Naphthalene sulfonate. The sizing dispersion is added to the raw material in an amount of 5 kg of AKD / metric ton of dry raw material. In Test 2, the sizing accelerator contains a condensed naphthalene sulfonate (available under the brand name Tamol®). And cationic starch with cationic substitution DS of 0.065 to nitrogen and fluorene group. In Test 1, cationic starch with cationic substitution of 0.065 without aromatic group and anionic inorganic silica particles provided in the form of a sol, that is, Anionic non-aromatic polymer is added to the raw material. The raw material used is based on 80% by weight of bleached birch / pine (60/40) sulfate pulp and 20% by weight of CaC03 refined to 200 CSF and contains 0.3 g / L of raw materials of Na2S04, with 461 microSiemens / cm conductivity coefficient and acid-base rhenium 8.1. Table 1 Test No. Anionic Sizing Dispersion / [Kg Sizing Agent / Metric Dry Material] Cationic Starch with Aromatic Group / [Kg / Metric Dry Material] Cation Starch (non-aromatic) / [kg starch / metric ton of dry raw material] Test 1 0.5 0 10 Test 2 0.5 10 0 Table 1 (continued) Test No. Condensed naphthalene sulfonate / [kg of condensate / metric ton dry raw material] Anionic oxidation Silicon particles / [Kg of oxidized sand / metric ton of dry raw materials] Cobb 60 / [g / m2] Test 1 0 1 4 5.2 Test 2 0 1 2 9.3 28 This paper size applies to China National Standard (CNS) A4 (210 X 297) Mm)------.------- # -------- Order --------- line-% Γ (Please read the notes on the back before filling (This page) 1226915 A7 _ B7 V. Description of the invention (V?) The sizing performance of the method of Example 2 was obtained by adding the same anionic sizing dispersion as described in Example 1 and containing a cation substituted with nitrogen. DS was 0.065. And a sizing accelerator for cationic starch and anionic inorganic silica particles (test 1) containing benzyl groups; and Accelerators for evaluation with condensed naphthalene sulfonate (available under the brand name Tamol®) and cationic starch with a cationic substitution DS of 0.065 and a fluorene group (Test 2) (cObb 60 test) However, calcium chloride is added to the raw materials to adjust the conductivity to 5000 micro-Siemens / cm to simulate raw materials with high conductivity. Table 2 Test No. Anionic Sizing Dispersion / [kg sizing agent / metric ton of dry raw material] Cationic starch containing aromatic group / [kg / metric ton dry raw material] Cationic starch (no aromatic group) / [kg starch / metric ton dry raw material] Test 1 0.5 0 12 Test 2 0.5 12 0 Table 2 (continued) Test No. Condensed naphthalene sulfonate / [kg of condensate / metric ton of dry raw material] Anionic silica particles / [kg of silicon oxide / metric ton of dry raw material] Cobb 60 / [G / m2] Test 1 0 1 .0 75 Test 2 0 1. 0 27.8 Example 3 The gluing performance was based on the use of AKD containing 15% of alkyl ketene dimer, 2% of cationic powder and A cationic sizing dispersion of 0.6% sodium lignosulfonate was evaluated. Ingredients and ingredients contained in the sizing accelerator 29 This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 public love) (Please read the precautions on the back before filling this page) #i ---- --Order --------- line temple -----! R -------------- 1226915 A7 _ B7 V. Description of the invention As shown in Table 3, it includes condensed naphthalene sulfonate, cationic powder with a DS of 0.065 without aromatic groups, cationic starch with a DS with 0.065 having aromatic groups, and anionic inorganic silica particles provided as a sol. The raw materials used were those of Example 2, which had an acid-base ratio of 8.1 and were added to the raw materials by calcium chloride to have a conductivity of 5000 microSiemens / cm. Table 3 Test No. Anionic Sizing Dispersion / [kg sizing agent / metric ton of dry raw material] Cationic starch containing aromatic group / [kg / metric ton dry raw material] Cationic starch (no aromatic group) / [kg starch / metric ton dry raw material] Test 1 0.5 0 10 Test 2 0.5 10 0 Table 3 (continued) Test No. Condensed naphthalene sulfonate / [kg of condensate / metric ton of dry raw material] Anionic silica particles / [kg of silicon oxide / metric ton of dry raw material] Cobb 60 / [G / m2] Test 1 0 1 5 5 Test 2 1 0 27.8 Example 4 A commercial substituted alkylketene dimer containing 8.9%, 0.89% of a DS with 0.065 and a substituted fluorenyl group was prepared. Anionic sizing dispersion of cationic starch and 0.22% condensed naphthalenesulfonate available under the brand name Tamol®. Anionic dispersion is added to a cellulose suspension (dry basis) containing 30% pine, 30% bees, 40% eucalyptus, and 15% deposited CaC03 in an amount of 0.0115% (dry basis) based on ketene dimer. 30 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- Order -------- -Line A7 1226915 V. Description of the invention U7). The conductivity of the suspension is 500 microSiemens / cm. Also added to the suspension was a sizing accelerator containing a benzyl substituted starch with DS of 0.065 and a condensed naphthalene sulfonate (Test 2) obtained under the trade name Tamol®. The same anionic dispersion was also added to the same suspension. However, the sizing accelerator added to the suspension does not contain aromatic polymers. The sizing accelerator contains a cationic starch with a DS of 0.065 and no aromatic group, and anionic inorganic silica particles provided in the form of a sol (Test 1). The polymer amounts of the accelerator and sizing agent (AKD) of the dispersion are shown in Table 4. (Please read the precautions on the back before filling out this page) ϋ HI ί-n nv. ---------------- Order --------- Line Table 4 Test No. anionic sizing dispersion / [kg sizing agent / metric ton of dry raw material] cationic starch containing aromatic group / [kg / metric ton dry raw material] cationic starch (without aromatic group) / [kg starch / metric ton dry raw material] 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 No. Condensed naphthalene sulfonate / [kg of condensate / metric ton of dry material] Anionic oxidized particles / [Kg of silica / metric ton of dry material] Cobb 60 / [g / m2] Test 1 0 0.120 9 0.0 Test 1 0 0.120 5 0.0 Test 1 0 0.120 2 9.0 Test 2 0.120 0 2 8.0 Test 2 0.120 0 27.0 Test 2 0.120 0 2 5.5 31 This paper size applies the Chinese National Standard (CNS) A4 (210 x 297 mm) 1226915 A7 _ B7 V. Description of the Invention (γ) Example 5 In this example, the same dispersion as in Example 2 is used Liquid and sizing accelerator, the difference is that the conductivity of the suspension is 5000 micro-Siemens /cm. The polymer amounts of the accelerator and sizing agent (AKD) of the dispersion are shown in Table 5. Table 5 Test No. Anionic Sizing Dispersion / [kg sizing agent / metric ton of dry raw material] Cationic starch containing aromatic group / [kg / metric_ dry raw material] cationic starch (without aromatic group) / [kg starch / metric ton dry raw material] ] Test 1 0.140 0 5 Test 1 0.160 0 5 Test 1 0.180 0 5.. _ Test 1 0.200 0 ........ Test 2 0.100 5 0.. ....... ....... Test 2 0.115 5 ......... Test 2 0.125 5 0 ___-.....- Test 2 0.140 5 0 _-- · … .. Test No. Condensed Naphthalene Sulfonate / [kg of condensate / metric ton of dry raw material]. Anionic silica particles / [kg of silica / metric ton of dry raw material] Cobb 6 〇 / [g / m²] Test 1 0 0.120 J ^ O_ Test 1 0 0.120 \ VL_ Test 1 0 0.120 _ Test 1 0 0.120 χϋ-…… Test 2 0.120 0 _ Test 2 0.120 0-Test 2 0.120 0 JJ_-. Test 2 0.120 0 _ 32 This paper size applies to China National Standard (CNS) A4 Specification (210 X 297 mm) (Please read the notes on the back before filling this page) -I i mate H9 nv m nw an < -------- Order .-- ------ line 1226915 A7 _______________ B7 five DESCRIPTION OF THE INVENTION (Chuan) The method of Example 6 by the glue lines used to evaluate the cobb 60 test. An anionic sizing dispersion containing an alkylketene dimer, a condensed naphthalenesulfonate, and bis (hydrogenated tallow) dimethylamine chloride was prepared. The sizing dispersion has an AKD content of 30% and contains bis (hydrogenated tallow) dimethylamine chloride at 4% based on AKD and condensed naphthalenesulfonate at 6% based on AKD. The sizing dispersion was added to the raw material in an amount of 0.3 kg of AKD / metric ton of dry raw material. Cationic starch with a cationic substitution DS of 0.065 and a benzyl group and a starch with a cationic substitution DS of 0.065 are used in combination with condensed naphthalenesulfonate and melaminesulfonate, respectively. The raw material used is based on 80% birch / pine (60/40) sulfate pulp and 20% by weight CaC03 refined to 200CSF and contains 0.3g / L of raw material NwSO4 with 555 Micro-Siemens / cm conductivity coefficient and acid-base ratio of 8.22. Table 6 Test No. Anion contains aromatic cations ~ Glue dispersion-based cation ionization powders (no fragrance / [kg saccharin starch / [based] / [kg glue / metric ton kg / metric ton powder / metric ton dry material] dry Raw materials] Dry raw materials] 'Test 1 0.3 10 Round — ~ -_ Test 2 0.3 10 Test 3 0.3 10 Test 4 0.3 10 —----- 33 This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) I .-- Γ * -------------- I --- Order · -------- (Please read the precautions on the back before filling this page ) 1226915 a7 _B7 V. Description of the invention (A) Test No. Condensed naphthalene sulfonate / [kg of condensate / metric ton of dry raw material] Anionic silica particles / [kg of silicon oxide / metric ton of dry raw material] Cobb 60 / [g / square M] Test 1 1 3 3 Test 2 1 5 2 Test 3 1 3 5 Test 4 1 6 8 14--rw ----------------- Order · ----- --- (Please read the notes on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 (210 x 297 mm)

Claims (1)

1226915 A8B8C8D8 VI. Application scope of patents where p is a polysaccharide residue; A is an atomic chain containing C and plutonium atoms that links N to the polysaccharide residue, and each of the heart and 112 is H or has 1 to 3 carbon atoms R3 is an aromatic hydrocarbon group; η is an integer from 2 to 300,000, and X · is an anion counter ion; and / or by polymerizing a cationic monomer or containing a cationic monomer represented by general formula (II) The vinyl addition polymer obtained from the monomer mixture: CH2 = C-Ri R2 (Π): C-Alm-Bj-N Q Rs whose center is H or CH3; each of R2 and R3 has from 1 to 3 Alkyl group of 1 carbon atom, A! Is 0 or NH, B! Is an olefin group or hydroxypropenyl group having 2 to 8 carbon atoms, Q is an aromatic group-containing substituent, and X_ is anionic Counter ion. 7. The method according to any one of items 1 to 4 of the scope of the patent application, characterized in that the cationic organic polymer is selected from a cationic polysaccharide having a structural formula ⑴: Ri. (Ux P — (— A—N_R_2) r R3 ( I) where P is a poly-It residue; A is an atomic chain containing C and Η atoms that links N to the polysaccharide residue; Ri and R2 are each 1 or a hydrocarbon group having 1 to 3 carbon atoms, R3 Is an aromatic hydrocarbon group 'n2 to 300,000, and X- is an anion counterion. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297mm f) (Please read the precautions on the back before filling this page ) One pack-1226915 i C8 D8 VI. Application for patent scope 8. The method according to any one of claims 1 to 4, which is characterized in that the anionic polymer is modified from a polymer of condensed naphthalene sulfonate type and modified The selected lignin polymer has been selected. 9. The method according to any one of claims 1 to 4 of the scope of patent application, characterized in that the sizing dispersion contains a cellulose-reactive sizing agent. 10. According to the application The method of item 9 of the patent is characterized in that the sizing dispersion contains There are acid anhydrides or ketene dimers. '11. The method according to any one of claims 1 to 4, characterized in that the sizing dispersion contains a cationic organic polymer having an aromatic group and / or An anionic polymer with an aromatic group selected by growing polymers, polysaccharides, and naturally-occurring aromatic polymers. 12. A method according to any one of the claims 1 to 4, which is characterized by the conduction of the suspension The coefficient is at least 3.5 milliSiemens / cm. 13. The method according to item 12 of the scope of patent application, characterized in that the conductivity of the suspension is at least 5.0 milliSiemens / cm. 3 ^ Paper ϋ Applies to Chinese national standards (CNS> A4 size (210 X 297 mm)! Γ ---- i ------------ ···· ... (Please read the precautions on the back before filling in this page), 1T: # · (I) 1226915 6. Scope of patent application 1. A method for sizing paper, comprising adding an anionic or cationic sizing dispersion to a suspension containing cellulose fibers and a selected paste, and containing an aromatic group Cationic organic polymer and anionic polymer sizing accelerator selected from gradually growing polymers, polysaccharides, and naturally-occurring aromatic polymers, characterized in that the sizing dispersion and the sizing accelerator are Self-addition to the aqueous suspension. 2. The method according to item 1 of the scope of patent application, characterized in that the cationic organic polymer and the anionic polymer are self-separately added to the aqueous suspension. 3. The method according to item 1 of the scope of patent application, characterized in that the anionic polymer is an aromatic polymer but the anionic polymer does not contain melamine or a derivative of melamine. 4. The method according to item 1 of the scope of patent application, characterized in that the anionic polymer is a nonionic polystyrene sulfonate which has an aromatic group but does not contain melamine or a derivative of melamine and is an anionic polymer. 5. The method according to any one of claims 1 to 4, wherein the cationic organic polymer is selected from a cationic polysaccharide or a cationic vinyl-based addition polymer. 6. The method according to any one of items 1 to 4 of the scope of patent application, characterized in that the cationic organic polymer is selected from cationic polysaccharides having the structural formula (I): Ri _ (ux P — (_ A-N-R_2 ) n R3 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before writing this page)