TW583378B - Process for the production of paper - Google Patents

Abstract

The invention relates to a process for the production of paper from an aqueous suspension containing cellulosic fibres, and optional fillers, which comprises separately adding to the suspension a cationic organic polymer having an aromatic group and an anionic polymer having an aromatic group, the anionic polymer being selected from step-growth polymers, polysaccharides and naturally occurring aromatic polymers and modifications thereof, forming and draining the suspension on a wire, with the proviso that if the anionic polymer is selected from step-growth polymers, it is not an anionic melamine-sulfonic acid condensation polymer. The invention further relates to a process for the production of paper from an aqueous suspension containing cellulosic fibres, and optional fillers, which comprises separately adding to the suspension a cationic organic polymer having an aromatic group and an anionic polymer having an aromatic group, forming and draining the suspension on a wire, with the proviso that the anionic polymer is not an anionic polystyrene sulfonate or anionic melamine-sulfonic acid condensation polymer.

Description

583378 A7 _ · _B7_ _-------- 5. Description of the invention (/) The present invention relates to paper making and more specifically to a method for making paper, in which cations and anionic polymers having an aromatic group are added to the paper making base. Half a bucket. This method provides improved drainage and retention. Background In the papermaking technology, an aqueous suspension containing cellulose fibers, which is called a raw material, and selected fillers and additives are fed into a headbox (headboy, which is used to discharge raw materials to a forming papermaking network. Water It is discharged from the raw material through the forming papermaking net so that the wet paper can be formed on the papermaking net, and the paper is further dehydrated and dried in the drying zone of the papermaking machine. It is usually called white water and contains, for example, microfibers and fillers. The water obtained from fine particles with additives is usually recovered in the papermaking process. Drainage and retention aids have traditionally been incorporated into raw materials to promote drainage and increase the adsorption of fine particles on cellulose fibers to interact with them. The fibers are retained together. Various drainage and retention aids are known in the art, such as anionic, nonionic, cationic and amphoteric organic polymers, anionic and cationic inorganic materials, and many combinations thereof. International patent applications Case notices W099 / 55964 and W099 / 55965 reveal drainage and retention aids containing cationic organic polymers with aromatic groups Cationic organic polymers can be used alone or in combination with various different anionic materials, such as anionic organic and inorganic condensation polymers, such as sulfonated melamine-formaldehyde and silica-based particles. It is advantageous for the papermaking method to provide improved drainage and retention. Provide cationic organic polymers with 4 improved drainage and retention. (Please read the note on the back first? Matters before filling out this page} 装 ---- ---- Order --------- Line 1 Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 583378 A7 ______ Β7 ___ 5. Description of the invention (2) Drainage of anionic polymer Stability and retention adjuvants are also advantageous. According to the present invention, it has been found that improved drainage and / or retention properties can be obtained by using a cationic organic polymer having an aromatic group and an anionic polymer having an aromatic group. Drainage and retention adjuvants are obtained. More specifically, the present invention relates to the manufacture of paper from aqueous suspensions containing cellulose fibers and optional fillers. A method comprising adding a cationic organic polymer having an aromatic group and an anionic polymer having an aromatic group to a suspension, the anionic polymer being selected from the group consisting of a step-growth polymer, a polysaccharide, and a naturally occurring aromatic Polymer and its improvement; forming on a papermaking web and discharging the suspension, provided that if the anionic polymer is selected from a gradual growth polymer, it cannot be an anionic melamine-sulfonic acid condensation polymer. The present invention Furthermore, the present invention relates to a method for manufacturing paper from an aqueous suspension containing cellulose fibers and an optional filler, which comprises separately adding a cationic organic polymer having an aromatic group and an anionic polymer having an aromatic group to In a suspension, it is formed on a papermaking web and the suspension is discharged. The premise is that the anionic polymer cannot be an anionic polystyrene sulfonate or an anionic melamine-sulfonic acid condensation polymer. The invention therefore relates to a method further defined in the scope of the patent application. As used herein, the term "drainage and retention aids" refers to two or more ingredients that, when added to an aqueous cellulose suspension, can obtain better drainage properties when less than two or more ingredients are added. And / or retention. The present invention applies 5 national paper standards (CNS) A4 specifications to paper materials from all types of materials, especially those with high content of salts (high conductivity) and colloidal substances, and / or in the papermaking method. 210 X 297 mm) (Please read the notes on the back before filling out this page) --- I ---- Order -------- .Line _ · 583378 A7 _____B7___; )) Improved drainage and / or retention can be obtained by making paper with a high degree of white water, that is, extended white water circulation and limited fresh water supply. The invention thus makes it possible to increase the speed of papermaking machines and use smaller amounts of additives to obtain corresponding drainage and / or retention effects, thereby obtaining an improved papermaking method and economic benefits. The invention also provides improved dry strength to paper. The cationic organic polymer having an aromatic group according to the present invention may be derived from natural or synthetic sources, and it may be of a linear, branched or cross-linked type. More preferably, the cationic polymer is water-soluble or water-dispersible. Examples of suitable cationic polymers include cationic polysaccharides, such as starch, guar, cellulose, chitin, chitosan, polysaccharides, galactan, polydextrose, gum resin , Pectin, mannan, dextrin, preferably starch and guar, suitable starches include potato, maize, wheat, cassava flour, rice, wax maize, barley, etc .; cationic synthetic organic polymers such as Cationic chain-growth polymers, such as cationic vinyl addition polymers such as acrylic, acrylamide, and vinylamine-based polymers, and polymers that grow cationically, such as cationic polyurethane . Cationic starch and acrylamide-based cationic polymers with aromatic groups are particularly preferred cationic polymers. The cationic organic polymer according to the present invention may have one or more aromatic groups' and the aromatic groups may be the same or different types. The aromatic group of the cationic organic polymer may be present on the polymer main chain (main chain) or on a substituent attached to the polymer main chain, preferably on the substituent. Examples of suitable aromatic groups include aromatic groups, aralkyl groups, and alkaryl groups, such as phenyl. 6 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm.) (Please read the back (Please fill in this page again)

--- IIII 丨 ^ IIIIII 丨 I 583378 A7 _______ _B7 V. Description of the invention (Zheng) (Please read the notes on the back before filling this page) phenylene, naphthyl, phenylene, xylylene, Benzyl and phenethyl; aromatic (aromatic) groups containing nitrogen, that is, pyridyl and quinic anhydride, and derivatives of these groups, preferably benzyl. 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 of the present invention, the cationic organic polymer having an aromatic group is a polysaccharide represented by the general structural formula (I):

Rt Ο) I X, P— (~ A, one M + — Q) π

I r2 where P is a polysaccharide residue; Ai is a group linking N to a polysaccharide residue, suitably an atomic chain consisting of C and Η atoms, and optionally 0 and / or N atoms, usually Is interrupted or substituted by an olefin group having from 2 to 18 and suitably from 2 to 8 carbon atoms, optionally with one or more heteroatoms such as 0 or N, such as alkoxy or hydroxy Propylene (-CH2_CH (OH) -CH2 ·); R! And r2 are each fluorene or, preferably, a hydrocarbon group, a suitable alkyl system having from 1 to 3 carbon atoms, suitably 1 to 2 carbon atoms ; Q is a substituent containing an aromatic group, preferably a phenyl group or a substituted phenyl group, which can be linked to an alkenyl group usually having from 1 to 3 carbon atoms, suitably 1 to 2 carbon atoms, On nitrogen, and Q is preferably a base group (CH2_C6H5); η is an integer, usually from about 2 to about 300,000, suitably from 5 to 20,000, and preferably from 6 to 125,000,000 or, in addition, R !, R2, and Q can be formed together with N to contain from 5 to 12 carbon atoms. 7 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297). Love 583378 A7 Γ ------------ Β7 V. invention is described ($) of the sub-aromatic group; a is an anionic counterion, usually similar _ chlorides thereof. Suitable polysaccharides represented by general formula ⑴ include those mentioned above. The cationic polysaccharides according to the present invention may also contain anionic groups, preferably in small amounts. This anionic group may be introduced into the polysaccharide through chemical treatment or may be present in the natural polysaccharide. According to another preferred embodiment of the present invention, the cationic organic polymer having an aromatic group is a chain-extending polymer. The term "chain-growth polymer" as used herein refers to a polymer obtained by chain-growth polymerization, and also refers to a chain-reactive polymer and a chain-reaction polymerization. Examples of suitable chain-growth polymers are Including vinyl addition polymers prepared by the polymerization of one or more monomers having vinyl or ethylene unsaturated chemical bonds, for example, by adding a cationic monomer containing a cationic monomer represented by general structural formula (II) Polymer obtained by polymer or monomer mixture: CHa ^ C —R, (II)

Ο = »Ο— · A? — · B2 -N Q X

I r2 wherein R3 is H or CH3; each of H and & is H or, preferably, a hydrocarbon group, suitably an alkyl group having from 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms: M is 〇 or NH; B2 is an alkyl or alkene group having 2 to 8 carbon atoms, suitably 2 to 4 carbon atoms, or a carbamoyl group; Q is a substituent containing an aromatic group, preferably Phenyl or substituted phenyl, which can be linked to the nitrogen via an olefinic group usually having from 1 to 3 carbon atoms, preferably 丨 to 2 carbon atoms, and Q is preferably ^ (< Η2_ 8 (Please read the precautions on the back before filling this page) -III — — — — · 11! 11111 * This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 583378 A7 ____ B7 — ― ― V. Description of the invention (A) C0H5); and X · are counterions of anions, usually similar to chloride compounds. Examples of suitable monomers represented by the general formula (II) include quaternary monomers, which are treated with benzyl chloride, such as [meth] acrylic acid dimethylaminoethyl, methacrylic acid diethyl Diethylaminoethyl and dimethylamine [meth] acrylic acid-dialkylamino alkyl [meth] acrylic acid and propyl methacrylate and, for example, methylaminoethyl [meth] acrylic acid Amine, diethylaminoethyl [methyl] propanamine, dimethylaminopropyl [meth] acrylamide, and diethylaminomethyl [meth] acrylamine Alkylaminoalkyl [meth] acrylamide is obtained. Preferred cationic monosystems of the general formula (I) include quaternary salts of dimethylaminoethylethyl-fluorenyl chloride and benzyl chloride quaternary salts of dimethylaminoethyl methacrylate. The monomer of formula (Π) may be copolymerized with one or more nonionic, cationic and / or anionic monomers. Suitable copolymerizable non-ionic monomers include [meth] acrylamide; such as n-alkyl [meth] acrylamide, N, N-dialkyl [meth] acrylamide and dioxane Acrylamide-based monomers such as dimethyamine, [meth] acrylic acid-based monomers, and diethylamino Suspected amine. Suitable copolymerizable cationic monosystems include quaternary salts of acid addition salts with dimethylaminoethyl [meth] acrylate and diallyldimethylammonium chloride. The cationic organic polymer may also contain anionic groups, preferably in small amounts. Suitable copolymerizable anionic monomers include acrylic acid, methacrylic acid, and various sulfonated vinyl monomers such as styrene sulfonate. Preferred copolymerizable monosystems include acrylamide and methacrylamide, that is, [meth] acrylamide, and the cationic or amphoteric organic polymer preferably uses acrylamide as the 9 paper size. China National Standard (CNS) A4 Specification (210 X 297 mm) (Please read the notes on the back before filling this page} · I-- 583378 A7 —------------- R7_ — _ V. Description of the invention (1) Basic polymer. The cationic vinyl addition polymer according to the present invention may generally contain k 1 to 99 mole%, suitably 2 to 50 mole% and preferably From 5 to 20 mole% of the cationic monomer having an aromatic group and from 99 to 1 mole%, suitably from 98 to 50 mole%, and more preferably from 95 to 80 mole%. A monomer mixture containing a copolymerizable monomer of acrylamide or methacrylamide ([meth] acrylamide), the monomer mixture suitably contains from 98 to 50 mole% and preferably From 95 to 80 mol% of methacrylamide, the sum of its percentages is 10 (). Suitable examples of the cationically increasing polymer according to the present invention Including cationic polyurethane, which can be prepared from a monomer mixture containing aromatic isocyanates and / or aromatic alcohols. Examples of suitable aromatic isocyanates include diisocyanates, such as toluene _2, 'with 2,6-diisocyanate and dibenzoyl-4,4'-diisocyanate. Suitable examples of aromatic alcohols include glycols, ie, diols, such as bisphenol A, phenyl Diethanolamine, triethylene terephthalate, and trimethylolpropyl monoterephthalate. For example, monohydroxy aromatic alcohols such as phenol and its derivatives can also be used. The monomer mixture can also contain non-aromatic Isocyanates and / or alcohols, usually diisocyanates and glycols, such as any producers known to be used in polyurethanes. Suitable monosystems containing cationic groups include, for example, acid addition salts and Such as 1,2-propanediol-3-dimethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, Nn-butyldiethanolamine and N-third butyldiethanolamine N-alkanediol dialkylamine and N-alkyldialkanolamine, N-stearin The quaternary product of diethanolamine and N-methyldipropanolamine is yang 10 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page ) · 111! 111 · 11111111 »583378 A7 _B7 _ 5. Description of the invention () Ionic diols. Quaternary products can originate from methyl chloride, dimethyl sulfate, benzyl chloride and epichlorohydrin alkane The weight average molecular weight of the cationic polymer can vary within wide limits, particularly depending on the type of polymer used, and it is usually at least about 5,000 and usually at least 10,000. More typically it is greater than 150,000, usually greater than 500,000, preferably greater than about 700,000, suitably greater than about 1,000,000 and most preferably greater than about 2,000,000. The upper limit is not important, it may be about 200,000,000, usually 150,000,000 and suitably 100,000,000. Cationic organic polymers may have a cationic substitution degree (DSc) that varies over a wide range, particularly depending on the type of polymer used; DSC May be from 0.005 to 1.0, usually from 0.01 to 0.5, suitably from 0.02 to 0.3, preferably from 0.025 to 0.2; and the degree of aromatic substitution (DSq) may be from 0.001 to 0.5, usually from 0.01 to 0.5 It is suitably from 0.02 to 0.3 and preferably from 0.025 to 0.2. In the case where the cationic organic polymer contains an anionic group, the degree of anion substitution (DSA) may be from 0 to 0.2, preferably from 0 to 0.1, and suitably from 0 to 0.05, and the cationic polymer has a full cationic charge. The charge density of the cationic polymer to the dry polymer is generally in the range from 0.1 to 6.0 meqv / g, preferably from 0.2 to 5.0 and suitably from 0.5 to 4.0. Examples of suitable cationic organic polymers having aromatic groups that can be used according to the present invention include those described in International Patent Publications WO 99/55964, WO 99/55965, and WO 99/67310, which are incorporated herein by reference. 11 This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) · 1111111 ^ — — — — — — — — 583378 A7 _______B7 5 2. Description of the invention (1) The anionic polymer having an aromatic group according to the present invention may be selected from a gradually growing polymer, a chain-growth polymer, a polysaccharide, a naturally occurring aromatic polymer, and modifications thereof. The term "gradually growing polymer" as used herein refers to a polymer obtained by gradually increasing polymerization, and also refers to a step-reactive polymer and a step-reactive polymerization, respectively. The anionic polymer is preferably selected from a gradually growing polymer, a polysaccharide, a naturally occurring aromatic polymer and modifications thereof, and most preferably a gradually growing polymer. The anionic polymer according to the present invention may be linear, branched or cross-linked. Preferably, the anionic polymer is water-soluble or water-dispersible. The anionic polymer is preferably organic. The anionic polymer according to the present invention has one or more aromatic groups, and the aromatic groups may be the same or different types. The aromatic group of the anionic polymer may be present on the main chain of the polymer or on a substituent attached to the main chain (main chain) of the polymer. Examples of suitable aromatic groups include aromatic groups, aralkyl groups and alkaryl groups and derivatives, such as phenyl, tolyl, naphthyl, phenylene, xylylene, benzyl, phenethyl and these Derivatives of groups. 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 will be negatively charged and acid groups that are negatively charged when dissolved or dispersed in water Here, the groups are collectively called anionic groups, such as phosphate, phosphonate, sulfate, sulfate, sulfonate, carboxylic acid, carboxylate, alkoxide and phenol group, that is, hydroxy-substituted phenyl and naphthyl group. . The negatively charged groups are usually salts of alkali metals, alkaline earth metals or ammonia. An example of a suitable anionic step-growth polymer according to the present invention is 12 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)

583378 B7 V. Description of the invention () Includes condensation polymers, that is, polymers obtained by gradually increasing condensation polymerization, such as aldehydes such as formaldehyde and one or more aromatic compounds containing one or more anionic groups, With other optional condensates of comonomers which can be used, for example, in the condensation polymerization of urea and melamine. Examples of suitable aromatic compounds containing anionic groups include benzene and naphthalene-based compounds containing anionic groups, such as phenol and naphthol compounds, such as phenol, naphthalene powder, resorcinol and derivatives thereof , Aromatic hydroxy acids and their salts, such as phenol, phenol, naphthalene and naphthol acids and their salts, usually sulfuric acid and sulfonate, such as benzene sulfuric acid and sulfonate, xylene sulfuric acid and sulfonate Naphthalene sulfate and sulfonate, phenol sulfate and sulfonate. Examples of suitable anionic step-growth polymers according to the present invention include anionic benzene-based and Tsai-based condensation polymers, preferably naphthalene-sulfuric acid-based and naphthalene-sulfonate-based Condensation polymer. Examples of further suitable anionic step-growth polymers according to the present invention include addition polymers, i.e. polymers obtained by a step-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. . Monohydroxy aromatic 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 diols, for example, any 13 paper sizes applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) " (Please read the precautions on the back before filling this page) · 1111111 · 1111! 111. 583378 A7 ___ B7_______ V. Description of the invention ((I) Known to be used in the preparation of polyurethane. Contains anionic groups Examples of suitable monomers include monoesters of triols such as Trimethylol Ethylene, Trimethylolpropane and Glycerol, and dicarboxylic acids such as succinic acid and anhydride, terephthalic acid and anhydride. Or the reaction product of its anhydride, for example, glyceryl monosuccinate, triglyceride monoterephthalate, trimethylolpropyl monosuccinate, trimethylolpropyl monoterephthalate, N, N-bis- (hydroxyethyl) -glycine, di- (hydroxymethyl) propionic acid, N, N-bis, (hydroxyethyl) -2-amineethanesulfonic acid, etc. are selected and usually used with alkali Reactions such as alkali metal and alkaline earth metal hydroxides, such as sodium hydroxide, ammonia or amines, such as Triethylamine, thereby forming a metal, soil, or counter ion. Examples of suitable anionic chain-growth polymers according to the present invention include those containing at least one monomer having an aromatic group and one having an anionic group. Anionic vinyl addition polymers obtained from at least one monomer based on vinyl or a mixture of ethylene unsaturated monomers are usually co-existed with nonionic monomers such as acrylic and acrylamide-based monomers Examples of suitable anionic monomers for polymerization include (meth) acrylic acid and p-vinylphenol (hydroxystyrene). Examples of suitable anionic polysaccharides include starch, guar gum, cellulose, chitin, Deacetylated chitins, polysaccharides, galactans, polydextrose, gum resin, pectin, mannan, dextrin, preferably powder, guar and cellulose derivatives, suitable for Starches include potatoes, maize, wheat, tapioca flour, rice, wax maize and barley, preferably potatoes. The anionic groups in the polysaccharides can be natural and / or chemically treated for feeding. The aromatic group in sugar can be guided by chemical methods known in the art. 14 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm). 1 ~-(Please read the precautions on the back before filling this page. )

583378 A7 —______ B7 ____ 5. Description of the invention (P-). The naturally occurring aromatic anionic polymer according to the present invention and its modification, that is, the modified naturally occurring aromatic anionic polymer are naturally occurring polymers including organic extracts of wood and bark of certain wood ingredients Phenolic substances and their chemical modifications are usually their sulfonated modifications. Modified polymers can be chemically treated to obtain, for example, sulfite pulp and cow hide pulp. Examples of suitable anionic polymers of this type include lignin-based polymers, preferably sulfonated lignin, such as lignosulfonate, kraft lignin, sulfonated kraft lignin, and tannic acid. Extracts. The weight-average molecular weight of the anionic polymer can vary within wide limits, particularly depending on the type of polymer used, and it is usually at least about 500, preferably above about 2,00 () and preferably It is higher than approximately 5,000. The upper limit is not important; it may be about 200,000,000, usually 150,000,000, preferably 500,000, 000,000, and preferably 10,000,000,000. 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, suitably from 0.02 to 1.8 and preferably Is from 0.025 to 1.5; and the degree of aromatic substitution (DSQ) can 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, and preferably from 0 to 0.05. The anionic polymer has all Its anionic charge. Generally, the anionic charge density of anionic polymers is from 0.1 to 15 on the paper size. The Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applicable (please read the precautions on the back before filling this page)- --11111 Order --------- " 583378 A7 ______B7_______ V. Description of the invention (f;) to 6.0 meqv / gram, preferably from 0.5 to 5.0 and more preferably from 1.0 to 4.0 〇 Examples of suitable anionic aromatic polymers that can be used in accordance with the present invention include those described in U.S. Patent Nos. 4,070,236 and 5,755,930; and International Patent Application Publications W095 / 21295, W095 / 21296, W099 / 67310, and WOOOM9227, It is included here for reference. Examples of the particularly preferred combination of an anionic and cationic polymer having an aromatic group as defined above according to the present invention include cationic polysaccharides, preferably cationic starch, and preferably anionic based on benzene. Polymers that gradually increase in anion with naphthalene-based condensation polymers, and anionic polyurethanes that are preferably anionic naphthalene-based condensation polymers; (ii) preferably cationic starch Cationic polysaccharides, naturally-occurring aromatic anionic polymers and modifications thereof, suitably anionic lignin-based polymers, preferably sulfonated lignin; (iii) suitable cationic vinyl compounds A cationic chain-growth polymer, preferably a cationic acrylamide-based polymer, and an anionic benzene-based and naphthalene-based condensation polymer, preferably anionic, step by step Growing polymers, and anionic polyurethanes which are preferably anionic naphthalene-based condensation polymers; and (iv) preferably anionic A vinyl addition polymer, a cationic fluorene-growth polymer suitable for cationic acrylamide-based polymers, and naturally occurring aromatic anionic polymers and modifications thereof, preferably 16 I paper size Applicable to China National Standard (CNS) A4 specification (210 X 297) '' '~ " (Please read the precautions on the back before filling this page) Installation -------- Order ----- ---- line f 583378 A7 ______ B7 _ 5. Description of the invention (porphyrin) Anionic lignin-based polymer, suitably sulfonated lignin; The cationic and anionic polymers according to the present invention are preferably separated It is preferable to add the cellulose fiber-containing aqueous suspension or raw material to the raw material at different points and not to form a mixture containing the polymer. The polymers can be added in any order. Although the reverse order of addition can also be used, usually cationic polymers are added to the raw materials first, and anionic polymers are added later. The polymer may be added to the raw material to be dehydrated in a wide range of amounts, particularly related to the kind of raw material, salt content, salt type, filler content, type of filler, addition point, and the like. Generally, the polymer is added in an amount that gives better drainage and / or retention than if it is not added, and usually the cationic polymer is added to the raw material before the anionic polymer is added. The cationic polymer is usually used to dry The starting material is added in an amount of at least 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 0.001% by weight, usually at least 0.005, of the dry raw material, but the upper limit is usually 3% and preferably 1.5% by weight. The polymer having an aromatic group according to the present invention can be mixed with Additional additives beneficial to overall drainage and / or retention are used together to form drainage and retention adjuvants containing three or more ingredients. Suitable examples of this type of raw material additives include anionic particulate materials, such as silica-based particles and montmorillonite-type clays, low molecular weight cationic organic polymers, aluminum compounds, anionic vinyl addition polymers and the like 17 (Please read the notes on the back before filling out this page) · III I--I · II I--I-- The size of this paper is applicable to China National Standard (CNS) A4 (210 x 297 mm) 583378 A7 ____ B7___ _ V. The compounds included in the description of the invention () and their uses are disclosed in International Patent Application Publications W099 / 55964 and W099 / 55965, which are incorporated herein by reference. The low molecular weight (hereinafter referred to as LMW) cationic organic polymer systems that can be used according to the present invention include those commonly referred to as anion fragmentation traps (ATC). LMW cationic organic polymers can be derived from natural or synthetic sources, and are preferably LMW synthetic polymers. Suitable organic polymers of this type include LMW highly charged cationic organic polymers, such as polyamines, polyamidoamines, polyethylenimines, and diallyldimethylammonium chloride. , [Meth] acrylamide and [meth] acrylic acid are both copolymers. Regarding the molecular weight of the cationic organic polymer having an aromatic group according to the present invention, the molecular weight of the LMW cationic organic polymer is preferably lower; it is preferably at least 2,000 and more preferably at least 10,000. The upper limit of the molecular weight is usually about 700,000, preferably about 500,000 and usually about 200,000. The aluminum compounds that can be used according to the present invention include alum, aluminates, aluminum chlorides, aluminum nitrates, and polyaluminum compounds, such as polyaluminum chloride, polyaluminum sulfate, and polyaluminum containing chloride and sulfate ions. Compound, polyaluminosilicate-sulfate, and mixtures thereof. The polyaluminum compound may also contain other cations other than chloride ions, such as cations derived from sulfuric acid, phosphoric acid, and organic acids such as citric acid and oxalic acid. The method of the present invention can be applied to all papermaking methods and cellulose suspensions, and it is particularly used for making paper from raw materials having a high conductivity. In this case, the conductivity of the raw material dewatered on the papermaking web is usually at least 2.0 milliSiemens / cm, preferably at least 3.5 milliSiemens / cm. 18 Mm) (Please read the notes on the back before filling this page) Order --------- line f 583378 A7 _______B7__ 5. Description of the invention (A) meters, and preferably at least 5.0 milliSiemens / cm . The conductivity can be measured by standard equipment, such as the WTW LF 5; 39 instrument supplied by Christian Berner. The aforementioned data are 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. The degree of high conductivity refers to the high salt (electrolyte) content, which can come from the materials used to form the raw materials, various additives in the raw materials, fresh water supplied to the method, and so on. Moreover, in large-scale recycling of white water, the salt content is usually high, which can lead to significant accumulation of salt in the process circulating water. The present invention further includes a papermaking method for large-scale recovery or recycling of white water, i.e., high levels of white water use, such as from 0 to 30 tons of fresh water per metric ton of dry paper, and generally less than 20, preferably less than 15, preferably less than 10 and especially less than 5 tons of fresh water. In the method, the white water recycling is preferably obtained by mixing white water with cellulose fibers and / or selected fillers to form a suspension to be dehydrated; preferably, the suspension enters the forming paper for dehydration. Before the netting, the white water was mixed with a suspension containing cellulose fibers and an optional tincture. White water may be mixed with the suspension before, during, or after the introduction of the drainage and retention adjuvants of the present invention. Fresh water can be introduced into the process at any stage; for example, it can be mixed with cellulose fibers in the form of a suspension 'and it can be mixed with a thick suspension containing cellulose fibers before, at the same time, or after mixing the suspension with white water to It is diluted in the form of a thin suspension to be dehydrated. 19 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling this page)---III--· I I ------ 583378 A7 _________ _B7 ___ 5. Description of the invention (| Γ |) Furthermore, the additives traditionally used in papermaking can of course also be combined with the polymers according to the invention, such as dry strengthening agents, wet strengthening agents, brighteners, dyes, coatings, etc. Gums, such as gums based on turpentine and cellulose-reactive sizing agents, such as alkyl and alkenyl ketene dimers, academic and alkenyl ketene multimers, and Succinic anhydride and so on. Cellulose suspensions, or raw materials, can also contain traditional types of mineral fillers, such as kaolin, magnetic clay, titanium dioxide, gypsum, talc and natural and synthetic carbonates, such as chalk, floor marble, and deposited calcium carbonate. The method of the invention is used in the manufacture of paper. The term "paper" as used herein, of course, does not necessarily include paper and its manufacture, but also other sheets or fabric-like products containing cellulose fibers, such as boards and cardboard and their manufacture. This method can be used in From papermaking containing different types of suspensions of cellulose fibers, the suspensions preferably contain at least 25% by weight of dry matter and preferably at least 50% by weight of fibers. The fibers of the suspension can be based on chemical pulp from, for example, sulfate pulp, sulfite and organosol, such as mechanical pulp, chemical-thermomechanical pulp, scouring pulp, and ground wood pulp from hardwood and softwood. It can also be based on recycled fibers, optionally from deinked pulp, and mixtures thereof. 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. Example 1 The cationic polymers used in the tests were either purchased on the market or prepared by commonly known procedures. 20 cationic polysaccharides used in the test The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) ------- -Order --------- · 583378 A7 B7 V. Description of the invention (β) is based on the general procedure described in EP-A0189935 and WO 99/55964 to react natural potato starch with a quaternary agent To prepare. The cationic polymers used in the tests are also collectively referred to as cationic polymers hereinafter. According to the inventors, C1 to C3, for comparison purposes, Cl-ref to C3-ref, which are as follows: C1: Borrow Cationic starch obtained by quaternizing natural potato starch with 3-chloro-2-hydroxypropyldimethylbenzyl ammonium chloride to 0.5% N. C2 · Cationic starch obtained by quaternizing natural potato powder and 3_chloro_2_ with propyldimethyl dry ammonium chloride to 0.7% N. C3: a cationic vinyl addition polymer having a molecular weight of about 100,000, prepared by polymerizing acrylamide (90 mole%) and acryloxyethyldimethylbenzyl chloride (10 mole%) .

Cl-ref: Cationic starch obtained by quaternizing natural potato starch with 2,3-epoxypropyltrimethyl chloride to 0.8% N. C2-ref: Cationic starch obtained by quaternizing natural potato starch with 2,3-epoxypropyltrimethylphosphonium chloride to 0.5% N. C3-ref. A cationic vinyl addition polymer having a molecular weight of about 6,000,000, prepared by polymerizing acrylamide (90 mole%) and acryloxyethyltrimethylammonium chloride (10 mole%). The anionic polymers used in the tests were purchased on the market or prepared by commonly known procedures. The anionic polymer used in the test is also collectively referred to as the anionic polymer hereinafter. According to the present inventors, A1 to A8, and for comparison purposes, Al-ref to Ahef are used as follows. Paper size applies Chinese National Standard (CNS) A4 g (21〇X 297 public love)-one-(Please read the precautions on the back before filling this page) -------- Order ----- ---- * § ^ is 583378 A7 ___B7____ 5. Description of the invention () A1: Anionic polycondensate of formaldehyde and naphthalene sulfonate with a molecular weight of about 20,000. A2: Anionic polycondensate of formaldehyde and naphthalenesulfonate with a molecular weight of about 110,000. A3: Anionic polycondensate with a molecular weight of about 40,000 of formaldehyde and tsasulfonate. A4: Anionic polycondensate having a molecular weight of about 210,000 of formaldehyde and naphthalenesulfonate. A5: By reacting glyceryl monostearate with toluene diisocyanate to form a prepolymer containing a terminal isocyanate group, it is then reacted with dimethylolpropionic acid to obtain an anionic polyurethane. A6: By reacting phenyldiethanolamine with toluene diisocyanate to form a prepolymer containing terminal isocyanate groups, which is then reacted with dimethylol. Propionic acid and N-methyldiethanolamine to obtain anionic polyamine groups Ethyl formate oA7: anionic sulfonated kraft lignin. A8: Anionic lignosulfonate.

Al-ref: anionic melamine-formaldehyde-sulfonate polycondensate. A2-ref: Anionic inorganic condensation polymer of silicic acid in the form of 5 micron particle size of colloidal silica particles. Low molecular weight cationic organic polymers also known as ATC used in some tests are commercially available and can be manufactured by commonly known procedures. ATC is as follows: ATC: Dimethylamine with a molecular weight of about 50,000 , Epichlorohydrin and B 22 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) --- 11 --- Order --- ------ 583378 A7 __ ___B7 —__ 5. Description of the invention (W) Cationic copolymer of enediamine. All polymers are used in the form of a dilute aqueous polymer solution. Example 2 Drainage performance can be evaluated by a Dynamic Drainage Analyzer (DDA) obtained from Akribi, Sweden. It is used to measure the set volume when the plug is removed and a vacuum is applied to the raw material on the other side of the mesh. The discharge time required for the raw materials to pass through the net. A standard raw material is bleached birch / pine sulphate pulp (60/40) with 56% by weight peroxide bleached TMP / SGW pulp (80/20), 14% by weight refined to 200 ° CST 30% by weight of magnetic soil. Add 25 g / L of the gum part and bleach from the paper press to the raw material. The raw material volume was about 800 ml and the pH was 7. Calcium chloride was added to the raw material to adjust the conductivity coefficient to 0.5 milliSiemens / cm. The obtained raw materials are called standard raw materials. An additional amount of calcium chloride was added to the standard raw materials to prepare a medium-conductivity raw material (2.0 milliSiemens / cm) and a high-conductivity coefficient raw material (0.0 milliSiemens / cm). Throughout the test, the raw materials were stirred at 1500 rpm in a septum jar and the chemical addition was performed as follows: i) the cationic polymer was added to the raw materials and then stirred for 30 seconds, ii) the anion The polymer is added to the raw material and then stirred for 15 seconds, iii) the raw material is discharged and the drainage time is automatically recorded. ATC, if used, is added to the raw material before i) adding the cationic polymer and ii) adding the anionic polymer according to the procedure described above and then stirring for 30 seconds. Table 1 shows various calculations based on the dry polymer versus dry raw material system. 23 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) I -------- $ ----- I --- 583378 A7 R7 V. Description of the invention (w) Different dosages of cationic polymer Cl, and different calculations based on dry polymer versus dry raw material system Dehydration (drainage) effect of doses of anionic polymers Al-ref, Al and A2. Standard materials are used in test numbers and high conductivity materials are used in test numbers 6-9. Table 1 Test number C 1 Dose [kg / ton] A Dose [kg / ton J Dehydration time [sec] A 1-ref A 1 A2 1 3 0 0 19.0 19.0 19.0 2 3 0 0.5 17.5 17.0 15.5 3 3 0 1. 0 14-6 12.6 12.1 4 3 0 2.0 12.8 9.0 8.4 5 3 0 3. 0 9.8 8.7 7.2 6 20 0 26.4 26.4 26.4 7 20 2.0 2 1.5 15.7 15.6 8 20 3. 0 17.6 14.6 13.7 9 20 4.0 15.7 14.5 13.4 Examples 3 For the first time, the turbidity of the white water obtained by discharging the filtrate from the dynamic drainage analyzer (DDA), that is, the raw material obtained in Example 2, was measured by a turbidimeter through a turbidimeter for evaluation. The results are shown in Table 2. Table 2 Test number Cl dose [kg / ton] A dose [kg / ton] Turbidity [NTU1 A 1-ref A 1 A2 1 3 0 0.5 5 6 49 5 5 2 3 0 1.. 5 5 5 0 5 0 3 3 0 2.0 52 47 4 8 4 3 0 3.0 5 0 43 4 5 24 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

Equipment -------- Order-I --- Line 1 583378 A7 B7 Table 3 V. Description of the invention (7.2) Example 4 Drainage performance is based on the use of cationic and anionic polymers according to Example 1 and according to Example 2 Standard materials and procedures to evaluate. The results are shown in Table 3. Test number C 1 Dose [kg / ton] A Dose [kg / ton] Dehydration time [seconds] A 1 A3 A4 1 0 0 18.0 18.0 18.0 2 20 0 12.5 12.5 12.5 3 20 1. 0 10.9 10.0 10.2 4 20 2.0 10.3 9.0 8.9 5 20 4.0 10.0 8.7 8.0 Example 5 Drainage performance was evaluated using the cationic and anionic polymers according to Example 1 and the conductivity raw materials and procedures according to Example 2. The results are shown in Table 4. Test number C 1 'Dose [kg / ton] A Dose [kg / ton] Dehydration time [sec] C 1 -ref Cl C2 1 10 0 13.8 14.6 11.5 2 10 0.75 12.6 10.6 7.4 3 10 1. 5 12.8 9. 5 6.6 4 10 3. 0 14.1 10.1 7.2 Example 6 Drainage performance was evaluated using cationic and anionic polymers according to Example 1 and high conductivity materials and procedures according to Example 2. The results are shown in Table 5. 25 This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) (Please read the precautions on the back before filling this page) Table 4 Packing -------- Order ----- ---- Line 1 583378 A7 ____B7 V. Description of the invention (ingenious) Table 5 Test No. C 1 Dose [kg / ton] A Dose [kg / nton] Dehydration time [second] A2 -ref A5 A6 1 2 0 0 3 1.8 3 1.8 3 1.8 2 20 1. 0 3 1.0 2 7.5 2 8.8 3 2 0 2.0 2 8.0 22.0 24.4 4 2 0 4.0 2 3.8 16.5 19.5 5 20 6.0 2 3.0 14.0 18.3 Example 7 The cationic and anionic polymers and the high conductivity materials and procedures according to Example 2 were evaluated. The results are shown in Table 6. Table 6 Test number C3 Dose [kg / ton] A Dose [kg / ton] Dehydration time [sec] A5 A6 1 2 0 15.8 15.8 2 2 0.25 13.8 13.3 3 2 0.5 13.2 12.9 4 2 0.75 13.4 13.1 5 2 1.0 13.5 13.3 Example 8 Drainage and retention properties were evaluated using cationic and anionic polymers according to Example 1 and standard conductivity materials and procedures according to Examples 2 and 3. The results are shown in Table 7. Test number C Dose [kg / ton] A7 Dose [kg / ton] When dehydrated ^ [sec. 1 / 荀 / turbidity [NTU] C 2-ref C 1 1 25 0 22.0 / 49 23.4 / 43 2 2 5 2 22.1 / 50 16.3 / 40 3 25 4 21.2 / 46 14.3 / 40 26 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) ^- ------ ^ --------- Test ATC C A8 Dehydration time / turbidity number dose dose dose [sec] / [NTU] [kg / ton] [kg / ton] [kg / ton ] C 3-ref C 3 1 3 3 2 21.4 / 49 11.1 / 40 2 3 3 3 17.4 / 46 9.3 / 40 3 3 3 4 15.6 / 48 8.9 / 45 583378 A7 B7 V. Description of the Invention (I) Example 9 Drainage Performance was evaluated using cationic and anionic polymers and ATC according to Example 1 and raw materials and procedures according to the conductivity coefficient in Example 2. The results are shown in Table 8. Table 8 Test ATC C A7 Dehydration time number Dose Dose dose [sec] [kg / ton] [kg / ton L [kg / ton] C3-ref C 3 1 3 3 1 20.8 11.0 2 3 3 3 3 3 1.5 17.9 14.7 9.3 7.9 Example 10 Drainage and retention properties were evaluated using cationic and anionic polymers and ATC according to Example 1 and conductivity materials and procedures according to Examples 2 and 3. The results are shown in Table 9. Table 9 Example 11 Drainage performance was evaluated using cationic and anionic polymers according to Example 1 and standard conductivity materials and procedures according to Example 2. The results are shown in Table 10. 27 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

IIIII Order II Table 1 0 Test CA 8 Dehydration time / turbidity number Dose dose [sec] / [NTU] [kg / ton] [kg / ton] C2-ref Cl 1 2 5 1 23.0 / 47 20.8 / 44 2 2 5 2 22.6 / 50 19.0 / 43 3 2 5 4 22.8 / 49 18.8 / 45 4 2 5 6 22.6 / 49 16.3 / 40 5 2 5 8 22.1 / 50 15.5 / 42 583378 A7 _B7 V. Description of the invention Applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

Claims (1)

"&Quot; --- j 1 rt $ A8 B8 modified replacement; 1 Y :: 2 /; pv. R-a C8 D8 standard · δ. Body 2 g 583378 VI. Application for patent scope I One for A method for manufacturing paper using plain fiber and a suspension of water and a raw suspension of selected tinctures, comprising adding a cationic organic polymer having an aromatic group and an anionic polymer having an aromatic group to the suspension, respectively. It is formed and the suspension is discharged, the premise is that the anionic polymer cannot be an anionic polystyrene sulfonic acid vinegar or an anionic melamine-sulfonic acid condensation polymer. 2. The method according to item 1 of the scope of patent application, its characteristics The cationic polymer is cationic starch. 3. The method according to item 1 of the scope of patent application, characterized in that the cationic polymer is a polymer based on acrylamide. 4. The method according to item 1 of the scope of patent application, which It is characterized in that the cationic polymer system has a weight average molecular weight of 10,000 to 100,000, up to 100,000. 5. According to the method of claim 1 in the scope of patent application, it is characterized by cation polymer It has a benzyl group. 6. The method according to item 1 of the scope of the patent application, characterized in that the anionic polymer is selected from an anionic benzene-based or naphthalene-based, progressively growing polymer that is a condensation polymer. 7. The method according to item 6 of the scope of patent application, characterized in that the anionic polymer is prepared from one or more aromatic compounds selected from phenyl, fluorene, naphthalene, naphthalene, and derivatives and mixtures thereof. 8 The method according to item 1 of the scope of patent application, characterized in that the anionic polymer is selected from naturally occurring aromatic polymers or modifications thereof. 9_ The method according to item 1 of the scope of patent application is characterized by anion ( Please read the notes on the back before filling this page.) The size of the bound paper is applicable to the Chinese National Standard (CNS) A4 (210 x 297 mm) 583378 B8 C8 D8. 6. The scope of patent application The polymer is selected from tannic acid extraction Substances, sulfonated lignin, benzenesulfuric acid, benzenesulfonate, xylenesulfate, xylenesulfonate, naphthalenesulfate, naphthalenesulfonate, phenolsulfate, phenolsulfonate and mixtures thereof. 10. Method according to item 1 of the scope of patent application, characterized in that the anionic polymer is selected from anionic polyurethane. 11. Method according to item 1 of the scope of patent application, characterized in that the anionic polymer has a range Weight average molecular weight from 500 to 1,000.000. 12. The method according to item 1 of the patent application range, characterized in that the cationic polymer is added in an amount of 0.005 to 2% by weight of the dry suspension. 13. The method according to item 1 of the scope of patent application, characterized in that the anionic polymer is added in an amount of 0.005 to 1.5% by weight of the dry suspension. 14. The method according to item 1 of the scope of patent application, further comprising adding a low molecular weight cationic organic polymer to the suspension. 15. The method according to item 1 of the scope of patent application, characterized in that the suspension has a conductivity of at least 2.0 milliSiemens / cm. 16. The method according to item 1 of the scope of patent application, characterized in that it further contains white water recycling and feeds from 0 to 30 tons of fresh water per ton of paper. 0 2 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back before filling this page)