WO1997023691A1 - Papermaking process - Google Patents

Papermaking process Download PDF

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Publication number
WO1997023691A1
WO1997023691A1 PCT/JP1996/003748 JP9603748W WO9723691A1 WO 1997023691 A1 WO1997023691 A1 WO 1997023691A1 JP 9603748 W JP9603748 W JP 9603748W WO 9723691 A1 WO9723691 A1 WO 9723691A1
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WO
WIPO (PCT)
Prior art keywords
polymer
soluble
water
anion
monomer
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PCT/JP1996/003748
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French (fr)
Japanese (ja)
Inventor
Tomonori Nakamura
Hideyuki Wakamatsu
Hidetoshi Sakamoto
Katsutoshi Tanaka
Original Assignee
Hymo Corporation
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Publication date
Family has litigation
Priority to JP7/350035 priority Critical
Priority to JP35003595A priority patent/JPH09176989A/en
Priority to JP8/19250 priority
Priority to JP01925096A priority patent/JP3218557B2/en
Priority to JP26377496 priority
Priority to JP8/263774 priority
Application filed by Hymo Corporation filed Critical Hymo Corporation
Publication of WO1997023691A1 publication Critical patent/WO1997023691A1/en
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27282557&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1997023691(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.

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    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06Paper forming aids
    • D21H21/10Retention agents or drainage improvers

Abstract

A papermaking process comprising the steps of: adding, to pulp for papermaking in the step of transforming pulp into paper in papermaking, an ionic water-soluble polymer prepared by a method wherein polymerization is conducted in an aqueous salt solution capable of dissolving monomers and incapable of dissolving the resultant polymer in the presence of a dispersant comprising a polyelectrolyte soluble in this aqueous salt solution while stirring to prepare a dispersion of fine polymer particles; and adding an anionic additive selected among anionic colloidal silica, anionic (co)polymers, bentonite, and mixtures thereof, thereby improving the yield and/or drainage rate. This process can markedly improve the yield of raw material/filler and the drainage rate, realizing a high quality and a high productivity.

Description

Specification

Extract paper how the art

The present invention relates to papermaking method in a papermaking process, more particularly Ion water-soluble polymer Contact and Anion colloidal silica of a particular production process the paper pulp in Sha paper process of papermaking, Anion soluble (co) polymer , yield and Roh walking by adding an Anion additive consisting chosen from a mixture of bentonite Bok Oyo patron relates Sha feeding method of improving the freeness. BACKGROUND

Conventionally, in a paper of the papermaking process, the composition distribution in the thickness direction of the paper layer was a problem that uneven by outflow of added various fillers. Also, increased cost due to the outflow of raw material 'added pressure chemicals, stock concentration was also to be solved problems such that becomes necessary above a certain value. Further, the outflow of the filler such as lead to contamination of the white water to be circulated. The addition of certain retention aid in order to solve these problems have been made. Also, improvement in papermaking speed during papermaking leads to improvement in productivity, whereas improvement of 叩 Kaido pulp is also desirable in terms of paper strength, but in conflict with machine speed, the solution to these at the same time it has been difficult. Contrast is aimed at solving Te cowpea addition of drainage aids. The retention aid or drainage aid, generally water-soluble polymer, Sunawa Chi Poriakuriruami de and its derivatives, polyethylene I Min, synthetic polymer materials such as polyamide Dobo triamine E Pic Rohi Dorin resin or, starch and natural water-soluble polymer such as a derivative thereof is used. The proposed various methods force the purpose of further improving the yield and Z or drainage. For example, cationic or method of papermaking by mixing added Koroidoshiri force after an amphoteric water-soluble polymer combined additive mixed (JP-3- 2 7 6 7 6 JP) to the stock, 2 5-6 0 mol% how the cationic starch Oh Rui after addition to the stock of Anion of Akuriruami de-based polymers having a molecular weight of from 00,000 to 1 0 0 Over 70 containing Anion groups of adding Hofmann reaction of polyacrylamide de (JP HirakiAkira 6 0 1 8 5 9 0 0 JP), a method using a cationic starch and Anion colloidal silica (JP 5 7 5 1 9 0 0 JP) acrylamide having a cationic group de system Po Rimmer a method using a colloidal silica (JP 6 2 - 1 5 3 9 1 JP), a method of adding a colloid silicic acid and cationic or amphoteric polyacrylamide de derivative and Kachio down starch ( JP 6 2 - 1 1 0 9 9 8 No. ), A method (JP-6 2-1 9 1 5 9 8 No.), etc. Various proposals to increase the yield by using Kachion of Helsingborg Ma one and bentonite Bok have been made. Further, the papermaking cellulosic slurry, a high molecular weight cationic polymer one added first, followed by pressurizing El papermaking method a medium molecular weight § anions polymer (JP-A-4 one 2 4 5 9 9 8 JP), the Kachion polymer flocculating agent filler yield enhancement method of adding the stock added Anion polymer compound after mixing and Ben Bok Nai mixtures Bok (Sho 6 4 - 6 1 5 8 8 No.), and the like. These methods t use a water-soluble polymer alone, Ru is increased or improved drainage of yield than the method has the been attempted, pulp of increased sophistication and wastepaper utilization Recent papermaking technology worsening circumstances, not be capable of satisfying sufficiently the reduction or the like of the paper water water quality, additional yield or filtration 7] improving method has been strongly desired. An object of the present invention improves the yield of cellulose fibers and fillers in the papermaking process, and by improving the Z or drainage is to improve Sha paper process, the productivity of the drying process. For more information, to produce a high quality paper aims to averaging in composition distribution in the thickness direction of the paper layer, it reduce the cost and prevent outflow of the materials and filler, also performs paper making high beating degree pulp If the Do reduce the papermaking speed, the objective things like. Another object of the present invention improves the yield, and / is ^, by keeping the white water to be circulated by improving the freeness clean is to establish a stable papermaking method. Furthermore, to improve the yield, and / it is had to provide a papermaking method of measuring the reduction of load in the white water recovery step by improving the drainage, to reduce the load in the wastewater treatment process. Disclosure of the Invention

The present inventors have found that in order to achieve these objects, the result of intensive studies, the papermaking papermaking process, adding and mixing Ion water-soluble polymer obtained by the following dispersion polymerization method to paper stock, followed by Anion colloidal silica, Anion soluble (co) polymer, by you admixing the Anion additive comprising selected from bentonite Bok and mixtures thereof, by papermaking process to improve the yield and Z or drainage, above Symbol object reaches the heading present invention can be achieved. The dispersion polymerization of the ionic water-soluble polymer used in the present invention, a water-soluble cationic vinyl represented by (A) the total monomer in the 3 to 1 0 0 mol% of the following formula (1) monomer or a mixture thereof, (B) the total monomer in 0-3 0 mol% of a water-soluble Anion soluble vinyl monomer, a monomer comprising a water-soluble nonionic vinyl monomer (C) residual , in an aqueous salt solution which does not dissolve the produced polymer was dissolved said monomer body, in the presence of a dispersant composed of soluble polymer electrolytic membrane to the salt solution, subjected to polymerization with stirring, a fine polymer it is a polymerization method for obtaining the partial dispersion liquid of the particles.

0 = CABN + -R 4 · - (1)

R

(Wherein, A is 0 or NH; B is C 2 H 4, C 3 H 6, C 3 H 5 OH; is H or CH 3; R 2, R 3 is CH 3 or C 2 H 5; R 4 is H, CH 3, C 2 H 5 or benzyl group;. X represents a Anion counter ion) Thus, the present invention is the paper pulp in the paper making process of paper, a monomer called dispersion polymerization dissolving Although dissolving the produced polymer Do, row polymerization of certain water-soluble Ion vinyl monomer with stirring in the presence of a dispersant composed of soluble polyelectrolytes to the aqueous salt solution in an aqueous salt solution and adding an ionic water-soluble polymer had it occurred in manufacturing the dispersion polymerization method to obtain fine polymer particles and then Anion colloidal silica, § two on-resistance (co) polymer, bentonite and a mixture thereof was added Anion additive to selected comprising, yield and / some Les, the improvement of drainage It is a papermaking method comprising Rukoto. The present invention, salt forms the aqueous salt solution used during the production of the ionic polymer used at the method, there is provided a 抄氏 wherein the divalent Anion salt . The present invention, the dispersant Ru used during the production of the ionic polymer used at the method, of 50 to 100 mole% dimethylaminoethyl § chestnut rate of salt, dimethyl § amino ethyl methacrylate click relay Bok of salt, dimethyl § amino professional buildings § acrylic § Mi de salt, salt of dimethyl § amino propyl methacrylamide § Mi de, § methacryloyl Ruo carboxymethyl E tilt trimethyl ammonium Niu Naked chloride de methacryloyl Ruo key shell tilt Li methylcarbamoyl Ruanmoniu Mukurori de, Akuriruami de pro building trimethyl ammonium Niu skeleton Li de, main evening Kuriruami de pro building trimethyl § emissions monitor © Solid port Li de, one selected from the group consisting of dimethyldi § Lil ammonium Niu Solid chloride de and mixtures thereof cation on monomer, and 0 to 5 0 mole% of a cationic high polymer electrolyte obtained by polymerizing acrylamide in There is provided a papermaking method which is characterized in that it. Papermaking Furthermore the present invention has an intrinsic viscosity of 2 wt% sulfuric acid Anmoniumu aqueous solution of the ionic water-soluble polymer In the method, to 5 d 1 Z g~3 0 d 1 der wherein Rukoto it is to provide a method. Furthermore, the present invention is the Ion water-soluble amount of the polymer stock SS per 0.0 0 1 - 0.2 wt%, the total amount of Anion additive is stock SS per 0.0 0 1 - there is provided a papermaking method which is a 0.5% by weight. In here, the amount of the ionic polymer is more preferably 0.0 0 1 - 0.0 5 wt%, the total amount of the Anion additives are 0.0 1 - 0.2 wt% is there. Further, a the Anion additive is Anion of adding after adding and mixing an ionic polymer (co) polymer in the present invention, the composition of the Anion soluble (co) polymer is, total monomers in the Akurinore acid 1 5-1 0 0 mole%, shall provide a papermaking method described above which is a polymerization product of monomers containing acrylamide 0-8 5 molar%. Further, the Anion additives added after adding and mixing an ionic polymer § two ON resistance (co) a polymer, as the Anion soluble (co) polymer by dissolving the monomeric product polymer is a papermaking method comprising the addition of water dilution of the dispersion of dissolved such ヽ saline solution line ,, resulting polymer fine particles polymerized in as the Anion additive a. The invention further includes wherein the process is added at, St. risks re Ichin previous papermaking process the Ion water-soluble polymer Te, the addition of the Anion additive after St. squirrel lean to provide a papermaking how to. The present invention, in the method, the ionic water-soluble polymer, in the paper making method characterized by comprising the total monomers in 1-3 0 mol% of a water soluble Anion soluble Bininore monomer is there. At this time, the Anion monomers, acrylic acid, methacrylic acid or their salts, Itakon acid or one of its salts, chosen from acrylamide dough 2 Mechirubu port pan sulfonic acid or a salt thereof and mixtures thereof more preferably Dearuko and Ca, and most preferably, acrylic acid. The present invention, at the method, gram equivalent number of the water-soluble force Chion vinyl monomer used in the ionic water-soluble polymer is greater than gram equivalent number of the water-soluble Anion vinyl monomer a paper making method, which is a monomer composition. The present invention, in the above method, les the ionic water-soluble polymer such contains a water-soluble Anio emissions of vinyl monomer, there is provided a papermaking method comprising things. Furthermore the present invention, the water-soluble nonionic vinyl monomer In the method, provides a papermaking method which is a Akuriruami de. The present invention also Sha paper the method at and before ¾ water-soluble cationic vinyl monomer, characterized in that a tertiary salt and / or quaternary product of di methyl amino ethyl § click Relay Bok it is to provide a method. BEST MODE FOR CARRYING OUT THE INVENTION

The method of producing an ionic water-soluble polymer used in the present invention, a water-soluble ionic vinyl monomer dissolves the Ion water-soluble polymer produced is soluble, such Ishio aqueous solution to be used, the aqueous solution in the presence of a dispersing agent consisting of soluble polyelectrolytes, it is to use a dispersing heavy legal to the polymerization of 攪 拌 while monomer to obtain a row ,, the Ion water-soluble polymer dispersion. And a method that is disclosed in European Patent Publication No. 1 8 3 4 6 6 No., or the European Patent Publication 3 6 4 1 7 5 No., etc. A method for manufacturing. The present inventors have found that the ionic water-soluble polymer prepared in dispersion polymerization in an aqueous salt solution, conventional polymerization method with the same monomer composition, for example, aqueous solution polymerization method, a water-in-oil emulsion polymerization legitimate in comparison with the manufacturing ionic water-soluble polymer, Anion colloidal silica, Anion soluble (co) polymer, when used in combination with bentonite and selected from a mixture comprising § two O emissions additive, markedly yield and leading to found the present invention Rukoto improve Z or drainage. This is considered to be due to the nature of dispersion polymerization in an aqueous salt solution. In the polymerization method, but before the polymerization the monomer is you are uniformly dissolved in an aqueous salt solution as a polymerization solvent, according to the polymerization proceeds, the resulting polymer has separated precipitated from an aqueous salt solution, with the aid of a dispersing agent to form a dispersion of fine particles. That is, phase separation force from homogeneous phase to 2-phase "is happening. The polymerization mechanism has not been clearly elucidated, but the aqueous solution polymerization method, a polymer of a special molecular structure that is different from the polymerization carried out in a polymerization force homogeneous phase as water-in-oil emulsion polymerization method, for example, branching is often polymer or proc copolymer force "is expected to be generated. The difference of this special molecular structure, can be expected to factors that increase the yield and Roh or drainage. Soluble force Chion vinyl monomer constituting the Ion water-soluble polymer used in the present invention are those represented by the following formula (1).

C Γ 2 = C- K 1 R 2

0 = C- A- B- N + - R 4 · X- ·, · (1)

I

Ra

(Wherein, A is 0 or NH; B is C 2 H 4, C 3 H 6, C 3 H 5 OH; is H or CH 3; R 2, R 3 is CH 3 or C 2 H 5; R 4 is H, CH 3, C 2 H 5 or benzyl group;. as X- represents an Anion counterions) water-soluble cationic vinyl monomer represented by the above formula (1) may, in particular, dimethyl tertiary salts chill § amino ethyl § click relay Bok there have dimethyl § amino ethyl methacrylate click relay Bok three quaternary salt and or quaternized or dimethyl § amino propyl acrylamide or dimethyl § amino professional building methacrylic Ami de, and / or quaternary product is preferred.

As the tertiary salt, hydrochloride or sulfate of said monomer is typically is a quaternized methylated in the monomer, Echiru halides and base Njiru compound are typical. Examples of the water-soluble cationic vinyl monomer represented by the concrete above formula (1), § methacryloyl Ruo key shell chill dimethylbenzyl ammonium Niu Naked chloride de, methacryloyl Ruo key shell chill dimethylbenzyl ammonium Niu Solid chloride de , acrylamide Dopurobi Le dimethylbenzyl ammonium Niu Naked chloride de, methacrylic Ami Dobro building dimethylbenzyl ammonium Niu Naked chloride de, § methacryloyl Ruo key shell tilt trimethyl-en Moni Umukurori de methacryloyl Ruo interleukin E tilt trimethyl ammonium Niu Naked chloride de, acrylic Ami Dobro building trimethyl § emissions monitor © Naked chloride de, Metakuriruami de-flop port building trimethyl ammonium Niu Naked chloride de, dimethylaminoethyl § chestnut rates hydrochloride or sulfate of dimethylaminoethyl main evening Kurire one Bok hydrochloride salt or sulfuric Salt, dimethyl § amino propyl hydrochloride or sulfate of acrylamide, such as dimethyl chill § amino propyl hydrochloride or sulfate of methacrylic § Mi de can be mentioned. Particularly preferred water-soluble cationic vinyl monomer Among these, § methacryloyl Ruo key shell chill dimethylbenzyl en Moniumukurori de as containing base Njiru group, as containing no benzyl group, § methacryloyl Ruo carboxymethyl Echiru a Bok trimethyl ammonium Niu 厶 Kurori de. Examples of the water-soluble Anion soluble vinyl monomer used in the present invention, for example, Itakon acid or its salts, maleic acid or its salts, fumaric acid or its salts, § click Lil system § Rui methacrylic Anion monomers or their the mixture can be a Ageruko of.

Akuriru system or as representative of methacrylic Anion monomers, eg if acrylic acid, methacrylic acid or its salt or 2-acrylamide dough 2-methyl propane sulfonic acid or its salt or mixtures thereof can be mentioned, et al, It is. In this, preferred water-soluble Anion vinyl monomers, acrylic acid, a Metakurinore acid, most preferably Akuriru acid. As the Ion water-soluble is used in a water-soluble polymer Nonion vinyl monomer of the present invention, for example, acrylamide or main evening Kuriruami de, hydroxy E chill § acrylate, hydroxyethyl E chill methacrylate. In terms of yield and z or drainage of a papermaking chemicals are used properly most preferred is acrylamide. Ionic water-soluble polymer used in the present invention, (A) the total monomer in 3 to 1 0 0 molar% of the formula (1) a water-soluble cationic vinyl monomer represented by or a mixture, (B) the total monomer in 0-3 0 mol% of a water-soluble Anion vinyl monomer, a monomer consisting of monomer composition ratio of the water-soluble Nonion vinyl monomer of (C) the remainder it is obtained by polymerizing. As the Ion water-soluble polymer used in the present invention, the force Chion soluble or amphoteric water-soluble polymer is preferably used. Anion colloidal silica, Anio emissions of (co) polymer, Anion additive comprising selected from bentonite and mixtures thereof are Anion properties, the polymer is added prior to the stock Anion of walking nonionic use of the water-soluble polymer is not preferable. If the Ion water-soluble polymer is a force Chion water-soluble polymer, water-soluble Kachion soluble vinyl monomer containing a benzyl group in the vinyl monomer represented by the above formula (1) more homopolymers or ones obtained by copolymerizing plural kinds or more water-soluble Roh two on vinyl monomers such as acrylamide or main evening Kuriruami de vinyl monomer represented by the above formula (1), preferable. These preferred have a molar ratio of the monomers is not particularly limited, resulting ionic water-soluble polymer does not dissolve in the polymerization solvent der Ru salt solution, i.e. the molar ratio of the monomers, such as salting-out is required Oh by the conditions. For example the Preferred ranges, the above formula (1) water soluble Kachion vinyl monomer containing a benzyl group in the water-soluble cationic vinyl monomer represented by or a mixture thereof 3 to 1 0 0 mol% , containing no benzyl group (1) represented by its other water-soluble cationic vinyl monomer or a mixture 0-5 0 mol%, and the balance of Nonion property consists monomer monomer polymer is a molar ratio such that salting. The monomer containing a benzyl group with a water-soluble cationic vinyl monomer of the above formula (1) is in Amino groups are bonded is a strong base Njiru group hydrophobic, so that although the water-soluble polymer not have summer less soluble in the salt solution. If therefore contain benzyl group-containing water-soluble force Chion vinyl monomer of the above formula to the components of the cationic water-soluble polymer (1) is is represented by the above formula does not contain a benzyl group (1) that it is possible to set a wide range of molar ratios of other water soluble force Chion vinyl monomer. On the other hand, in the case of Kachion water-soluble polymer to the water-soluble Kachion soluble bi two Le monomer represented by the above formula does not contain a benzyl group as the water-soluble cationic vinyl monomer (1) to component the the molar ratio of the water-soluble cationic vinyl monomer and acrylamide or main evening Kuriruami de 3: 9 7-3 0: 7 0 preferred range. As an ionic water-soluble polymer used in the present invention, amphoteric water-soluble polymer and a water-soluble cationic vinyl monomer or a mixture 3-9 9 mol% represented by the above formula (1), wherein the water-soluble Anion 0 mole% sexual vinyl monomer 1-3, water-soluble nonionic vinyl monomer remaining, for example, even the is obtained by copolymerizing acrylamide or methacrylamide Ami de, more preferred. These preferred molar ratio of monomers was form force student not particularly limited polymer does not dissolve in aqueous salt solution as a polymerization solvent, i.e. the molar ratio of the monomers, such as salting-out is a prerequisite. However in order to show the features of the amphoteric water-soluble polymer is a cationic, all Ion resistance bicycloalkyl two Le monomers including Anion is laid it preferred that contained 5 mol% or more in the copolymer, 1 0 mol% more preferably it contained more. Yield and total ionic vinyl monomer is less than 5 mol% in the copolymer, the various properties such as freeness becomes insufficient. Regarding each ionic vinyl monomer molar ratio of Kachion group of the amphoteric copolymer is for better force Ku preferably larger than Anion group, gram equivalent value of the water-soluble force Chion of vinyl Honoré monomer it is preferred to larger consisting gram equivalent value of the water-soluble Anion vinyl monomer. Particularly preferably, the cationic group is more than twice the least Anion gram equivalent value of the group. More preferred examples of the above amphoteric water-soluble polymers, for example, a water-soluble cation on vinyl monomer containing a benzyl group in the water-soluble cationic vinyl monomer represented by the above formula (1) or mixtures thereof 3-9 9 mol%, other water-soluble cationic vinyl monomer represented by the above containing no benzyl group (1) or a mixture 0-5 0 mol%, the water-soluble Anion soluble vinyl monomer mer 1-3 0 mol%, and a monomer other than the components in the total monomer can be mentioned dispersion copolymer of monomers consisting Akuriruami de.

Other Other preferable examples of the amphoteric water-soluble polymer, for example, water-soluble cationic vinyl monomer or a mixture thereof 3 to 3 0 mol represented by the above formula does not contain benzyl Le group (1) %, Anion monomer 1-3 0 mol%, monomers other than pre words himself component in the total monomer can and Ageruko the dispersion copolymer of monomers consisting Akuriruami de. Further, monomers other than these, for example, Akurironitoriru, Mechiruakurire one Bok, E chill § chestnut rate, 2 Echiru hexyl § chestnut rate, the hydrophobic monomer be formed copolymer of styrene and the like water-soluble if so, also possible Mel be copolymerized. The polymerization is carried out with stirring plurality monomer in an aqueous salt solution in the presence of a dispersing agent, this monomer concentration at preferably not less than 5 wt%, more preferably 1 0% by weight or more, 1 5 4 0% by weight is particularly preferred. Economically preferable because the monomer concentration is polymer concentration in the dispersion is less than 5% by weight lower. A polymerization solvent during the production of the polymer used in the present invention, for the aqueous salt solution as a dispersion medium, the polymerization product is not dissolved, i.e. Ru important condition der be salted. That this condition is satisfied, the monomer composition of the ionic water-soluble polymer, the type of salt, the combination of the concentration of salt is important. Salts for use in an aqueous salt solution, multivalent Anion salts are preferred. As the typical, such as sodium sulfate, sulfate Anmoniumu, magnesium sulfate, aluminum sulfate, and mosquito disodium hydrogen phosphate and the like. In these other salts, dissolved monomers and a dispersing agent can be used so long as it does not dissolve the polymerization product. Of these, sulfates are preferred. In addition, in terms of the valence, divalent Anio Nshioka "preferred. Specifically, the most favorable preferable particularly Anmoniumu and sodium sulfate. Salt concentration in the reaction solution during the polymerization, the water-soluble cationic vinyl Le monomer represented by the above formula (1), and the molar ratio of water-soluble Anion vinyl monomer, kind of salt used different because by etc., it is not particularly limited.

However, usually, the salt concentration in the reaction solution during polymerization is 1 5 wt% or more based on the polymerization solvent, excluding the weight of the monomers from the weight of the polymerization reaction liquid, up to the limit of or solubility to the saturation concentration range are preferred, 1 5 wt% to 3 0% by weight and more preferably less, 1 5 wt% or more 2 5 wt% or less is particularly preferred. The viscosity of the reaction solution becomes high polymerization reaction with the salt concentration is less than 1 5% by weight is difficult. Salt is polymerized by adding to the solvent at the time of polymerization, part of the salt after the polymerization, it may be added to the dispersion. Than polymerized by adding salt at once into a solvent at the time of polymerization, the salt - after part of the completion of the polymerization, force who were added to the dispersion <Ru can reduce the viscosity of the dispersion. After completion of the polymerization part of the salt, the salt concentration in the dispersion obtained by adding to the dispersion 1 5% by weight or more, preferably in the range of up to the limit of or solubility to the saturation concentration, more preferably 1 5-2 5 percent by weight. Monomers of various types of salts, the polymerization product is salted out Shinano even by changing the concentration of the salt L, the set formed and monomers, salts folding of the polymerization product does not cause Ion water-soluble polymer type of body composition and salt, the combination of concentration is unsuitable. Dispersant polyelectrolyte coexist during polymerization is soluble in the aqueous salt solution is a mandatory condition. As the polymer electrolyte, the product terms cationic polymers are preferred and as an ionic polymer which is, gram equivalent value of the cationic monomer therein in the case of the amphoteric polymer of Anion monomer large made it preferable than the graphene 厶当 quantity value, therefore, the use of cationic polyelectrolyte is preferred. As the dispersing agent, 5 0-1 0 0 mol% of dimethyl § amino ethyl § chestnut, single Bok salts, salts of dimethyl § amino ethyl methacrylate, salts of dimethyl § Mino professional building acrylamide, dimethyl § Mino Pro Birume Takuriruami de salt, § methacryloyl Ruo key shell tilt trimethyl ammonium Niu 厶 Kurori de, main evening methacryloyl Ruo key shell tilt trimethyl ammonium Niu Naked chloride de, Akurirua mi de trimethyl § emissions 乇 Niumukurori de, methacrylic Ami Dopurobirutori methyl ammonium Niu Naked chloride de, one cationic monomer selected from the group consisting of dimethyl § Lil ammonium Niu Solid chloride de and its mixtures these, and 5 0-0 mol% obtained by polymerizing acrylamide cationic polyelectrolyte is more preferred. Relative to the amount of the polymer amount of dispersant electrolyte Zentan monomers is approximately 1-1 5 wt%, further from about 1 to 1 0 wt% Ca preferred. In less than 1% by weight polymer product dispersed form, not obtained by state, undesirably become large lumps attached to one another. Since 1 5 used in an amount exceeding the weight percent is sometimes free-flowing, the higher the finally obtained viscosity of the dispersion itself may be lost, which is undesirable. In the present invention, initiation of the polymerization reaction, the resulting polymer if the state of the dispersion may be used any kind of known methods. However, it is good preferable to use a polymerization initiator. There is no particular limitation requirements force the selection of a polymerization initiator ", generally Furirajika Le initiator is preferably used. These polymerization initiators, redox system, § zone system, or is suitably selected from those of the other systems. Is a redox initiator, Pas one Okiso sulfate Anmoniu 厶, potassium Pas one Okiso sulfuric acid, hydrogen peroxide, and either peroxide Benzoiru, sodium bisulfite, ferrous, tetramethyl Echirenjiamin sulfate, either dimethyl § aniline the combination of whether, and the like. The § zone-based initiator, 2, 2 '- Azobisu (2-amidinopropane) dihydric Dorokurori de, 2, 2' Azobisu [2- (2-imidazolin-one 2-I le) propane] dihydric Dorokurori de, 2, 2 '- § zone bis isoprene Ciro nitrile, 2, 2' - Azobisu (2, 4-dimethyl-Barre Roni Bok Lil), and 2, 2 '- Azobisu (4 main Toki Sea 2, 4-dimethyl-Barre Roni Bok Lil ), and the like. Other types of initiators, Paokiso sulfate Anmoniu 厶, potassium Pas one Okiso sulfate, peroxide Hydrogen peroxide Asechiru, lauroyl peroxide, base peroxide Nzoiru, Kumenhai Doropa - peroxide, di Isseki over-tert-Bas one oxide, Te Bok La methyl thiuram disulfide, dibenzo I Le disulfinate de, p- toluenesulfonic acid and the like et be.

Moreover, lever to effect proper polymerization initiator at a selected temperature in the present invention, there is no particular limitation on the polymerization temperature. The type of the polymerization initiator, 2, 2 '- Azobisu (2-amidinopropane) dihydric Dorokurori de, 2, 2' Azobisu [2- (2-imidazolin-one 2-I le) propane] Jihidorokurori de like water-soluble point is, handleability, preferably used from the viewpoint of controllability and the like. Ion water-soluble polymer concentration in the polymer dispersion is a high concentration of more than 5 wt%, but is generally about 40 wt% 5 wt% or more. Note the dispersion contains a dispersing agent in the salt and above. The above dispersions containing a high concentration of Ion water-soluble polymer, but Ion water-soluble polymer whose viscosity so are stably dispersed in an aqueous salt solution in the form of fine particles is low, usually 10 ~ 3000mP since a low viscosity of a · S, it flows easily, have very take manageable features. The average particle size of the ionic water-soluble polymer particles in said dispersion is usually 0.. 1 to 0.99 m, preferably from 0. l~50 / zm, more preferably 0. l~30 m. On average particle size of the ionic water-soluble polymer particles that lack precipitated storage stability since easy Kunar exceeds 150, since the ionic water-soluble polymer particles be mixed with water is greater when using dispersion solubility is poor, which required a long time to completely dissolve in. The molecular weight of Ion water-soluble polymer in the dispersion described above is not particularly limited. However, when used in papermaking papermaking process, the molecular weight is preferably larger. When dissolved a dispersion of an ionic water-soluble polymer in 2% by weight sulfuric acid Anmoniumu solution, the intrinsic viscosity of the polymer is usually in the range of about 5 dl / g ~ 3 0 dl Z g. Yield and or drainage effect and the intrinsic viscosity is less than 5 dl Z g is insufficient, 3 0 dl Z g larger than texture deteriorates, adversely affect the quality of the product. The above dispersion is excellent in storage stability, it does not cause problems such as to agglomerate Te particles adhere Gotsu be stored at room temperature. The Anion additives used in the present invention, Anion colloidal silica, Anion soluble (co) polymer, are those selected from bentonite and mixtures thereof. Anion colloidal silica used in the present invention has been produced by holding the aqueous solution of Orutogei Sansoichida to p H 1 to 4, it can also be used for the in circulation as a normal commercial product . Anion colloidal silica force is dioxide Kei arsenide at normal water having 0 H groups by Ri surface hydration, the particle surfaces are negatively charged (1) generally in water porous. Specifically, for example, JP-5 7-5 1-9 0 0 No. surface area described in Japanese about 5 0 to about 1 0 0 0 m 2 g, preferably about 3 0 0 to about 7 0 O m 2 Zg colloidal Gay acid sol having silica particles, may be mentioned colloidal silica force containing the colloidal Gay acid sol from about 2 0-9 0%. Also has an extension only in one plane at a substantially uniform thickness ranging from about 5 to 2 0 nm, and an elongated particle diameter measured by dynamic light scattering method of about 4 0~ 3 0 0 nm, Anion of silica force sol shape can be used preferably. For even bentonite Bok, it can be used which are distributed as normal commercial products. Anion soluble (co) polymer is a (co) polymer containing § two on monomer containing Anion substituent on the monomer in. At this time, as the Anion monomer, Akurinore acid, methacrylic acid or their salts, Itakon acid or salts thereof, maleic acid or salts thereof, fumaric acid or a salt thereof, acrylamide dough 2-methyl propane sulfonic acid or it is preferably one selected from a salt thereof and mixtures thereof. The most preferred Anion monomers are acrylic acid, i.e. as a § two ON resistance (co) polymer of acrylic acid (co) polymer is preferably used. Further, monomers other than these, for example Metakuriruami de, Akurironitoriru, main Takuriro two Bok Lil, methyl § chestnut rates, methyl methacrylate, Echiruakuri rate, E chill methacrylate, hydroxy Ne chill § chestnut rates, such as hydroxyethyl E chill methacrylate nonionic it is also possible to copolymerize sex monomer. The Atariru acid (co) polymers, Polymerization preferably the composition total monomer in Akuriru acid 1 5-1 0 0 mole%, monomers containing acrylamide 0-8 5 mol% that it is preferable ones. There is no particular limitation on the production method of Anion of (co) polymer used in the present invention can be prepared by conventional known methods. Among them is preferably a single-mers polymerized in an aqueous salt solution which does not dissolve the dissolves to produce (co) polymer is the polymerization method for obtaining the polymer fine particles. The molecular weight of the obtained Anion soluble (co) polymer is preferably 1 5 0 10,000 or more. Adding aqueous dilution of the obtained polymer in this manner to the stock. Papermaking process Nio Te, the addition amount of Ion water-soluble polymer is 2 wt% 0.1 from the stock SS per 0.1 0 0 1 wt%, the sum of the amount of the Anion additive stock 0. 0. 0 0 1 wt% per SS 5% by weight. Furthermore, the ionic additive amount of the water-soluble polymer is a stock SS per 0.0 0 1 wt% to 0.0 5 wt%, the amount of total force of Anion additives "stock SS per 0 . 0 1% to 0.2% by weight is more preferable. When chemical additive amount is too small to effect reduction, also the contamination of the felt or wire to be used in the papermaking process is excessive likely to occur. In paper making process according to the invention, is not particularly limited addition timing of each additive, was first added an ionic water-soluble polymer, followed by Anion colloidal silica, Anion soluble (co) polymer, bentonite Bok and it is necessary to add Anion additive comprising selected mixtures thereof. Preferably, in the papermaking process, and adding an ionic water-soluble polymer of the papermaking process prior centriscreen, Anion colloidal silica, Anion soluble (co) polymer, comprising selected bentonite Bok and mixtures thereof or al Anion arbitrariness preferred that the addition of a sexual additives after St. Li screen.

After addition of Ion water-soluble polymers, preferably be polymer suspended material surface by moderate shear is evenly distributed. Further, Anion colloidal silica, Anio emissions of (co) polymer, bentonite Bok and Anion additives after the addition of the composed chosen from the mixture, it is desirable to avoid disruption of the aggregates due to excessive strong stirring. The present invention, ionic water-soluble polymer prepared in dispersion polymerization in an aqueous salt solution having the same monomer composition, conventional polymerization method, for example, an aqueous solution polymerization method, in water-in-oil emulsion polymerization compared to an ionic water-soluble polymer produced, Anion colloidal silica force, Anion soluble (co) polymer, when used in combination with bentonite Bok and selected from a mixture comprising § two O emissions additive, markedly yield and Z or, as previously described for Ru improve drainage, the dispersion polymerization method in an aqueous salt solution, an aqueous salt solution strength as a polymerization solvent, according et polymerization proceeds, the produced polymer separates precipitated. Polymers of three-dimensional molecular structures different from one to the polymerization polymerization for this is performed by uniform one phase, for example, branching multi have polymer is produced, the difference between the three-dimensional molecular structure, yield and or drainage It can be expected to factors that improve. Example

Then examples will be specifically described the invention, the present invention as long as not exceeding the gist thereof, is not intended to be bound by the following examples.

(Preparation Examples of ionic polymer)

(N o. 1~6)

Stirrer, sulfuric thermometer, separator trouble flask, fitted with a reflux condenser, one liter of five-neck equipped with a nitrogen inlet tube, polyacryloyl Ruo key shell tilt trimethyl-en Moniumukurori de 4. 2 g as a dispersant, as a precipitation agent take Anmoniumu 8 4. O g, and dissolved by adding ion-exchanged water 3 0 3. O g. It was charged with the monomers 1 0 0. O g of the composition described in Table 1, while warming to 5 0 ° C, it was purged with nitrogen. This 2, 2 'as a polymerization initiator - Azobisu (2-amidinopropane) dihydric Dorokurori 1% aqueous solution of de 2. O g was added, under stirring, 1 0 hours and polymerized at 5 0 ° C, dispersed in an aqueous salt solution polymer microparticles was obtained. The reaction solution was dissolved by adding sulfuric acid Anmoniumu of 2 1 g, to obtain a dispersion polymer samples A ~ F for use in the present invention.

The intrinsic viscosity of the sulfuric acid Anmoniu 厶 aqueous solution of monomers one composition and 2% by weight of the dispersion polymer samples A ~ F are described in Table 1.

(N o. 7~1 2)

The ratio down similarly using monomers one composition described in Table 1 for, to give a comparative sample a~f in Table 1, wherein an aqueous solution polymerization and reversed-phase Emarujiyon polymerization.

i 較試 charge a ~ monomer composition and 2% by weight of f the intrinsic viscosity of the sulfuric acid Anmoniumu aqueous solution described in Table 1.

【table 1】

※ ABC: § methacryloyl Ruo key shell chill dimethylbenzyl ammonium Niu 厶 Kurori de DMQ: § methacryloyl Ruo key shell tilt trimethyl ammonium Niu Solid chloride de

A lambda c: Akuriru acid A Am: acrylamide (Preparation Example of acrylic acid (co) polymer)

Stirrer, reflux condenser, thermometer, five B separable flask 5 0 0 ml equipped with a nitrogen inlet tube, deionized water 1 4 5. 5 g, density 5 0 weight percent acrylic § Mi de solution 9 6 g, Akuriru acid 1 2 g, was charged sulfate Natoriumu 4 6. 5 g, was adjusted to 2 5 ° C on a water bath, and stirring for 30 minutes nitrogen. To this was added a concentration of 1 0% by weight of the persulfate Anmoniumu solution 0.6 ml, concentration 1 0 wt% sodium bisulfite aqueous solution 0.6 ml as a polymerization initiator, conducting polymerization while continuing 攒拌If, it became cloudy after two minutes. Remove the water bath at this point, the heat of polymerization by 3 0 minutes after about 7 0. Become C. Then, 2 hours, holding the Polymerization temperature water bath of 7 0 ° C, to complete the polymerization reaction. The viscosity of Akuriru acid acrylamide copolymer thus obtained, Burukkufu I - a 3 2 0 m P a 's in the field viscometer, the results of microscopic observation, an average flow dispersion of spheres Kai 5 m It had become. This dispersion (polymer concentration 2 0% by weight) was diluted to 4 0 fold with de I O emissions water was measured for viscosity on a Brookfield viscometer, a 3. O m P a · s, the polymer dissolved It did not. The Borima one was neutralized with sodium hydroxide of, by measurement of intrinsic viscosity in chloride Na Bok Riumu aqueous 1N was 6. O dl Zg. The dispersion of acrylic acid 'acrylamide copolymer and sample G. Also created a homopolymer one dispersion of Akuriru acid by the same method. This dispersion is designated as Sample H. Specific viscosity in a 1N aqueous solution of sodium chloride in the neutralization of the sample H is 6. A 1 d 1 / g. (Examples 1 to 14)

Ivy a test that measures the yield rate by adding ionic polymer dispersion (A) ~ (F) to the stock. Hardwood bleached kraft pulp (L- ΒΚΡ) [Canadian 'Standard' pretend one Ness (CS F) = 330] heavy calcium carbonate as a filler in a 15 wt%

(Pulp) was added, and adjusted to a SS concentration 0.5 wt%.

Using this slurry one by Britt-type dynamic jar tester one was measured yield rate. The test KoTsuta by the following procedure.

The 0.5 wt% stock 500 meters 1 charged into split type dynamic jar tester.

1500 r Stirring was started at pm, adding a cationic polymer 0.1 by weight% aqueous solution obtained in Preparation Example. It starts counting from the time this.

After 30 seconds, 0.1 wt% bentonite (trade name: Oganozo one Boo 0, Arai Dokoroido Co.) and Bruno or 0.1 wt% § two on colloidal silica (trade name: BMA-780, Nissan Ekanoberu Co. ) is added.

After a further 30 seconds, open the cock for white water harvesting, to running water white water that has passed through the 150me shwire.

Discard the white water of the initial 10 seconds, to collect white water then 30 seconds. During this time of white water amount to Xm 1.

The white water was filtered in advance 105 ° dry weight at C (W.g) quantitative filter paper are measured (Toyo Roshi Kaisha, Ltd. NO. 5 C), and dried at 105 ° C, a weight Measure. This weight and Wig.

Then, incineration at 600 ° C, measuring the ash weight. This weight and fg. Determine the SS concentration and the ash concentration in the white water by the following equation (

Wl one Wo

White water SS concentration (wt%) = X 100 = S Si

X f

Ash concentration in the white water (wt.%) = XI 00 = A sh!

X

For even 0.5 wt% stock, similarly SS concentration, to measure the ash concentration. It respectively, and SS 0, A s ho.

SofuTome rate and obtaining the filler yield ratio by the following equation.

SofuTomeritsu = X 100

(T-OPR%) S So

Λ sh o- A shi

Filler walking Tomeritsu = X 100

(F-0PR%) shown in Table 2 summarizes the results obtained A s ho. [Table 2]

(Comparative Examples 1 to 14)

Used in Example 1-14, by using the polymer dispersion (A) ~ solution polymerization evening Eve polymers and E Mar job type polymer instead of (F) (a) ~ ( f), carried out It was measured yield rate in the same manner as in examples 1-14. The results are shown in Table 3. Composition of the polymer, The properties in Table 1. [Table 3]

(Example 15 to 30)

Used in Examples 1-14, the ionic polymer dispersions (A) ~ using (F), § two on colloidal silica and or Ben Bok Nye Akuriru acid in place of Bok (co) polymer sample (G ), (H) and / or with bentonite bets were measured yield rate in the same manner as in example 1-14.C Table 4 the results obtained are shown in Table 4

(Comparative Example 15 to 30)

Used in Comparative Examples 1 to 14, ionic polymers (a) ~ with (f), Anion colloidal silica and Roh or bentonite instead acrylate (co) of Bok polymer sample (G), (H) and using Roh or bentonite was measured yield rate in the same manner as in Comparative example 1 to 1 4. The results are shown in Table 5.

[Table 5]

(Example 31 to 44)

It was drainage test by adding ionic polymer dispersion (A) ~ (F) to the paper making pulp. Cardboard wastepaper: Newspaper wastepaper 90:10 pulp mixture of (CS F = 300) was adjusted to 1 wt% pulp concentration, further adding a liquid aluminum sulfate 3 wt% (pulp), was a pH of 5.8 .

The slurry one 30 Om 1 taken 50 Om 1 beaker at a three-one motor, 600 r pm while stirring force et at, 0 of the polymer obtained in Preparation Example 1~ 6 (A) ~ (F) . addition of 1 wt% aqueous solution. After 30 seconds, the addition of 0.1 wt% § two on copolyester Roidarushirika and Z or 0.1 wt% bentonite Bok. After a further 3 0 seconds, stirring was stopped, transferring the slurry to a 1 liter graduated cylinder one. After a one liter the total amount at Shimizu, performs a fall stirring three times, to put into Canadian 'bystander de freeness tester. According hand CS de measurement, measures the filtrate amount to out flow to the side tube.

The results obtained are shown in Table 6.

[Table 6]

40 D 300 0 500 495

41 E 300 0 500 505

42 F 300 0 500 502

43 A 300 1 00 300 5 1 3

44 D 300 1 00 300 570

(Comparative Example 3 1-44)

At polymer dispersion (A) - ionic polymer (a) the same manner as in Example 3 1-44 using ~ a (f) a method in place of (F) used in Example 3 1-44, to measure the drainage amount i <^ - o

The results are shown in Table 7.

[Table 7]

Ionic Anion copolyester D Ida bentonite

Or Comparative Example Polymer Rushiri amount amount drainage amount

Type amount 删 transliteration SS) (删 SS) (ml)

SS) (ppm) (ppm) (ppm)

3 1 a 200 200 0 442

32 b 200 200 0 452

33 c 200 200 0 446

34 d 200 200 0 435

35 e 200 200 0 455

36 f 200 200 0 443

37 a 300 0 500 460

38 b 300 0 500 465

39 c 300 0 500 463

40 d 300 0 500 450 41 e 300 0 500 470

42 f 300 0 500 460

43 a 300 100 300 470

44 d 300 100 300 462

(Example 45 to 60)

Used in real Sfi example 31 to 44, the ionic polymer dispersions (A) ~ using (F), § two on colloidal silica and / or bentonite Akuriru acid in place of Bok (co) polymer sample (G ), (H) and or by using a bentonite Bok was measured drainage volume in the same manner as in example 31 to 44. The results obtained be shown together in Table 8.

[Table 8]

Ionic bentonite sample. Sample H

Example Polymer amount amount amount drainage amount

Type amount (vs. IFFL (thigh SS) (organ SS) ■ SS) (m 1)

SS) (ppm) (ppm) (ppm) (ppm)

45 A 250 0 150 0 478

46 B 250 0 150 0 472

47 C 250 0 150 0 482

48 D 250 0 150 0 478

49 E 250 0 150 0 480

50 F 250 0 150 0 470

51 A 250 0 0 150 476

52 B 250 0 0 150 474

53 C 250 0 0 150 480

54 D 250 0 0 150 480 55 E 250 0 0 150 478

56 F 250 0 0 150 474

57 A 250 250 80 0 513

58 D 250 250 80 0 505

59 A 250 250 0 80 514

60 D 250 250 0 80 506

(Comparative Examples 45-60)

Used in J Comparative Examples 31-44, the ionic polymer (a) ~ with (f), Anion colloidal silica and Z or acrylic acid in place of bentonite (co) polymer sample (G), (H) and with Z or bentonite was measured yield rate in the same manner as in Comparative example 31 to 44. The results are shown in Table 9. [Table 9]

5 4 d 2 5 0 0 0 1 5 0 4 4 0

5 5 e 2 5 0 0 0 1 5 0 4 4 6

5 6 f 2 5 0 0 0 1 5 0 4 4 4

5 7 a 2 5 0 2 5 0 8 0 0 4 8 3

5 8 d 2 5 0 2 5 0 8 0 0 4 7 5

5 9 a 2 5 0 2 5 0 0 8 0 4 8 4

6 0 d 2 5 0 2 5 0 0 8 0 4 7 susceptible of 6 industrial

The papermaking process of the present invention, to improve the Ri yield of cellulose fibers and fillers in the papermaking process, and or it is possible to improve the drainage, thereby improving the productivity in the papermaking process, a drying step can. Further, the papermaking how the present invention, the white water that circulates can be kept clean, further, it is possible to achieve reduction in load in the white water recovery step, the reduction of the load in the wastewater treatment process.

Claims

The scope of the claims
1. In the papermaking process the paper, was added and mixed with an ionic water-soluble polymer obtained by the following step to the stock, followed by Anion colloidal silica, Anion soluble (co) polymer, comprising selected from bentonite and mixtures thereof by adding mixed-the Anion additive, a paper making process to improve the yield and z or drainage, the manufacturing process of the Ion water-soluble polymer, (a) the total monomer in 3-100 water-soluble cationic vinyl monomer or mixtures thereof represented by the following formula in mole% (1), (B) the total monomer in 0 to 30 mol% of a water-soluble Anion soluble vinyl monomer, (C ) a monomer comprising a water-soluble nonionic vinyl monomer remaining, and the product polymer was dissolved said monomer body in an aqueous salt solution which does not dissolve, the soluble polymer electrolyte salt solution dispersed in the presence of the agent, while stirring Performed if, Sha sheet wherein that it is a polymerization method for obtaining a dispersion of fine polymer particles.
0 = CABN + -R 4 · X (1)
R;
(Wherein, A is 0 or NH; B is C 2 H 4, C 3 H 6, C 3 H 5 OH; R t is H or CH 3; R 2, R 3 is CH 3 or C 2 H 5; R 4 is Π, CH 3, C 2 H 5 or benzyl group; X- represents an Anion counterions).
2. papermaking method according to claim 1, wherein the salt forming the aqueous salt solution is a divalent Anion salts.
3. The dispersing agent, 50 to 100 mol% of dimethylaminoethyl § chestnut rate of salt, dimethylaminoethyl meth click relay Bok salts, salts of dimethyl § amino propyl § chestnut Ruami de, dimethyl § amino professional building main evening Kuriruami de salt, Akuriroiruo key shell tilt trimethyl ammonium Niu Naked chloride de, main evening methacryloyl Ruo key shell tilt trimethyl ammonium Niu Naked chloride de, acrylamide professional building trimethyl ammonium Niu 厶 Kurori de, methacrylic Ami Dopuropiru Bok Rimechiruanmoni Umukurori de, one cationic monomer selected from the group consisting of dimethylol distearate § Lil ammonium Niu Solid chloride de and mixtures thereof, and 0 to 50 mole% of the cationic polyelectrolyte obtained by polymerizing acrylamide papermaking process according to paragraph 1 to claim 2, characterized in that it.
4. The ionic water-soluble polymer, any of 2 wt% sulfuric acid Anmoniumu solution intrinsic viscosity 5d l during, G~30d 1 / claims, characterized in that g is the first term to 3, wherein paper-making method of crab described
5. The ionic polymer additive amount 0.5 per stock SS from 001 to 0. 2% by weight, the total amount of the Anion additive is 0.001 to 0.5 wt% per pulp SS papermaking method according to any one of claims 1 to fourth terms, characterized in that.
6. The 0.001-0 addition amount per stock SS ionic polymer. 05% by weight, previous remarks himself 0.01 to per total addition amount stock SS of Anion additive 0. 2% by weight papermaking method according to claim 5, wherein Rukoto Oh.
7. Anion additives added after adding and mixing the Ion polymer is an Anion of (co) polymer composition of the Anion soluble (co) polymer is a Akuri Le acid total monomer 1 5-1 0 0 mol%, the paper according to any one of claims paragraph 1 - paragraph 6 which is a polymer of monomers containing Akuriruami de 0-8 5 mol% Method.
8. Anion additives added after adding and mixing the ionic polymer is an Anion of (co) polymers, as the Anion soluble (co) polymer, dissolving the resulting polymer was dissolved monomer Sina, range the items 1 to Ί claims, characterized in that the addition of water dilution of the dispersion polymerization in an aqueous salt solution line L ,, resulting polymer fine particles as the Anion additive papermaking method according to any one of items.
9. The Ion water-soluble polymer was added to Sen Bok Li screen before the papermaking step a, before Symbol range 囲第 items 1 to 8 claims is characterized by the addition of Anion additive after St. squirrel lean papermaking method according to any one of items.
1 0. The ionic water-soluble polymer, claim 1, wherein, characterized in that it comprises the total monomers in 1-3 0 mol% of a water soluble Anio emissions of vinyl monomer, second papermaking process according to what Re of Section 9.
1 1 1. The Anion monomer is, acrylic acid, methacrylic acid or their salts, Itakon acid or a salt thereof, or acrylamide one 2-methylpropane sulfonic acid selected from a salt thereof and mixtures thereof papermaking process according to paragraph 1 0 wherein the claims, which is a species.
1 2. The Anion monomer is, papermaking methods ranging first one of claims claims, characterized in that acrylic acid.
1 3. gram-equivalent number of the water-soluble cationic vinyl monomer used in the ionic water-soluble polymer is greater than gram equivalent number of the water-soluble Anion vinyl monomer, it is a monomer group formed wherein the papermaking method according to any one of claims 1 through Section first two terms.
1 4. papermaking method according to any of the ionic water-soluble polymer is a water-soluble Anion claim 1, wherein characterized that have not name contains vinyl monomer to 9, wherein
1 5. papermaking method according to any of claims the items 1 to 1 4, wherein, wherein the water-soluble nonionic vinyl monomer stamina acrylamide.
1 6. The water-soluble cationic vinyl monomer is dimethyl § amino ethyl § click the items 1 to 1 5 wherein claims, characterized in that a relay bets of a tertiary salt and Roh or quaternized papermaking method according to any one of.
PCT/JP1996/003748 1995-12-25 1996-12-24 Papermaking process WO1997023691A1 (en)

Priority Applications (6)

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JP7/350035 1995-12-25
JP35003595A JPH09176989A (en) 1995-12-25 1995-12-25 Paper making method
JP8/19250 1996-01-11
JP01925096A JP3218557B2 (en) 1996-01-11 1996-01-11 Paper-making method
JP8/263774 1996-09-13
JP26377496 1996-09-13

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DE1996607394 DE69607394D1 (en) 1995-12-25 1996-12-24 A process for the production of paper
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EP96942614A EP0877120B2 (en) 1995-12-25 1996-12-24 Papermaking process
AT96942614T AT191026T (en) 1995-12-25 1996-12-24 A process for the production of paper
AU20118/97A AU2011897A (en) 1995-12-25 1996-12-24 Papermaking process

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US6818100B2 (en) 2000-08-07 2004-11-16 Akzo Nobel N.V. Process for sizing paper
US7250462B2 (en) 2001-06-11 2007-07-31 Hymo Corporation Amphoteric water-soluble polymer dispersion and use thereof
US7189776B2 (en) 2001-06-12 2007-03-13 Akzo Nobel N.V. Aqueous composition
US7091273B2 (en) 2002-05-07 2006-08-15 Akzo Nobel N.V. Process for preparing a polymer dispersion
EP1835074A4 (en) * 2004-12-28 2010-04-07 Toagosei Co Ltd Composition for yield improver
JP6293170B2 (en) 2013-01-11 2018-03-14 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se The method of manufacturing paper and paperboard
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EP0877120A4 (en) 1999-03-03
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